WO1994004592A1 - Photoconductive polymers - Google Patents

Abstract

The invention relates to polymers which exhibit excellent electronic, optical and mechanical properties. The invention more particularly relates to polymers of the polyquinoline and polyanthrazoline class which are useful in electronic, optoelectronic and photonic applications. The invention further relates to a method of solubilizing polymers of the invention and polyquinolines and polyanthrazolines in general, using a complexing agent of a Lewis acid, a dialkyl phosphate, a diaryl phosphate or mixtures thereof.

Description

PHOTOCONDUCTIVE POLYMERS

The present invention relates to photoconductive polymers. More specifically, the invention relates to a series of polymers and copolymers in the polyquinoline and polyanthrazoline class which have electrical and optical characteristics well-suited for electronic, optoelectronic and photonic applications. The present invention is also directed to a method of solubilizing these polymers, and polyquinolines and polyanthrazolines in general, in a manner which facilitates processing of the same into configurations important for practical implementation.

2. Description of the Prior Art

Polymers, or macromolecules, are generally thought of as insulators for electrical purposes and have found widespread use accordingly. However, advances in electronics, optoelectronics and photonics have created a practical need for polymers that exhibit electronic and optical properties suitable for use in commercially important devices, such as electrophotographic copying and facsimile machines, laser printers, light- emitting diodes, flexible displays, optical switches and waveguides.

Among the polymeric materials that have been investigated in this regard are those having an unsaturated backbone, such as polyacetylene, which has been a particular object of scrutiny. Polyacetylene can be prepared using Ziegler-type catalysts to form a freestanding insoluble flexible film and, when properly doped, can exhibit metallic-like conductivity. The utility of polyacetylene is, however, limited for practical purposes: it is unstable, reacting with air and moisture to the detriment of its photoconductive character, and is intractable to a point where it cannot be readily processed into fibers , thin films etc. --that is, those configurations and geometries needed for most applications.

Efforts to ameliorate the drawbacks inherent to polyacetylene have been undertaken, but have met with only marginal success. Thus to improve processability, an approach wherein one or more polyacetylene-precursor compounds are processed, rather than polyacetylene per se, is known. In this technique, the precursors are soluble, which permits fabrication of fiber and thin- film geometries as well as a variety of other shapes. Although adequate solubility is obtained with this approach, the chemistry involved is extensive and complicated, making this method hard to implement in any practical fashion. Moreover, although the precursors are generally stable in the presence of air and moisture, they are, in the ordinary course, exposed to heat during processing, which can result in conversion to polyacetylene.

Another polymer that has been investigated is polythiophene. Like polyacetylene however, polythiophene exhibits poor processability. One technique to enhance polythiophene processability involves the incorporation of soluble side chains, usually very long ones, into the polymer. The inclusion of such side groups imparts sufficient solubility to the polythiophene to permit processing into the requisite shapes. However, while the addition of side groups in this manner aides the processing of polythiophene, it adversely affects the mechanical properties of that polymer and moreover causes a loss in thermal resistance by transforming the polymer into a low temperature material, i.e., one that has a glass transition temperature (T_G) slightly above room temperature. This loss of mechanical integrity and high temperature stability has made this side-chain approach less-than-desirable from a practical stand-point.

Finally, polymers other than polyacetylene and polythiophene have been investigated in the hope of eliminating, or at least minimizing, problems of the sort associated with the latter. Among the better-known polymers that have received attention in this regard are polyphenylene vinylene (PPV), polythiophene vinylene (PTV) and polyvinyl carbazole (PVK). While these particular polymers have proved utile in a variety of applications, their electronic and optical properties -- especially their nonlinear optical properties; that is, the disproportionate optical behavior evinced consequent to interaction with electromagnetic radiation-- are less than ideal. Thus for example, although commonly used in imaging applications, such as electrophotographic copying, PVK has a "dark" conductivity, i.e., conductive behavior in the absence of light, that is less than optimal.

One family of polymers that have been of especial interest are the polyquinolines, as represented, for example, by poly(2,6-(4-phenylquinoline)) known hereafter as "PPQ"; poly(2,2'-(biphenylene)-6,6'-bis(4-phenylquinoline)) known hereafter as "PBPQ"; poly(2,2'-(p,p'- stilbene)-6,6'-bis(4-phenylquinoline)) known hereafter as PSPQ; and poly(2,2'-(1,4-phenylene)-6,6'-bis(4-phenylquinoline)) known hereafter as "PPPQ". Closely relat ed to this family of polymers are polyanthrazolines, as represented, for example, by poly(2,7-(p,p'-biphenylene)-4,9-diphenyl-1,6-anthrazoline) known hereafter as "PBDA"; and poly(2,7-(1,4-phenylene)-4,9-diphenyl-1,6-anthrazoline) known hereafter as "PPDA". All of the aforementioned polymers generally exhibit high thermal stability (> 550°C) and excellent mechanical properties.

Despite these attributes, these polymers are not easily processed into useable configurations, including fibers, thin films, free-standing objects and the like. Part of the problem in this regard is that these types of polyquinolines and polyanthrazolines are not generally soluble in organic solvents. Indeed, many of these materials are not even soluble in strong acids, such as suifuric acid, methane sulfonic acid and trifluoromethane sulfonic acid. As solubility is an all-important factor in the ultimate ability to use these polymers in a practical sense, several attempts have been made to improve the same.

Thus, flexible linkages, such as -CH₂-, -O-, -S-, etc. have been introduced into the polymer structure in an attempt to increase solubility. While this leads to improved solubility in organic solvents, it also detracts from the desired properties thus resulting in polyquinolines that are not useful for the intended purpose. Another approach, similar to that tried for polythiophene, has involved the attachment of long side groups to the polyquinoline chain. Unlike polythiophene, however, this technique does not enhance the solubility of polyquinolines to any marked degree. Finally, and similar to the tact taken with polyacetylene, a precursor route to a rigid-rod conjugated polyquinoline has been attempted. This particular approach, however, is highly specific and places an enormous restriction on the flexibility in selecting diverse polymer structures and, in consequence, is not a viable practical approach to the solubilizing and processing of polyquinolines and the related polyanthrazolines.

While polyquinolines are not generally soluble in organic solvents, they are soluble at high concentrations in a solvent system consisting of di-m-cresylphosphate (DCP) dissolved in m-cresol, which system is commonly employed as the polymerization medium for these polymers. Although the polyquinolines can be processed into thin films and fibers from DCP/m-cresol solutions, there are inherent problems with this solvent system which prevent it from becoming used on a large scale. First, DCP is not generally available and is difficult to synthesize and purify. Second, solutions of polyquinolines in DCP/m-cresol are highly viscous even at low concentrations (< 0.5 wt. %) and thus do not lend themselves to conventional processing techniques, such as spin coating onto a substrate to create a thin film. Moreover, the solvent m-cresol is difficult to remove, which processing of polyquinolines into high quality, uniform thin films extremely complicated. Lastly, there is no convenient method for preparing optical-quality, uniform, free-standing films from these polymers that are suitable for practical use.

Thus while polyquinolines and polyanthrazolines as a whole show promise for electronic, optoelectronic and photonic applications, there continues to be a pressing need to develop polymers having improved electrical, optical and physical characteristics as well as for an improved method of processing these types of polymers that is simple, flexible, reliable, cost effective, repeatable and capable of being implemented on a large scale.

The present invention is directed to a polymer generally of the polyquinoline and polyanthrazoline class that exhibits improved electrical and optical properties than polymers known heretofore. In addition, the polymer of the present invention manifests excellent heat resistance and moisture stability thus permitting its utilization in a variety of applications and environments. Importantly, the structure of the polymer of the present invention may be modified in a predetermined fashion to obtain desired physical, electrical and/or optical properties, such as having maximum optical absorption or photoconductivity in any desired region of the electromagnetic spectrum, including the visible and near infrared regions.

In accordance with the present invention, a polymer is provided comprising a repeating unit of structure (I) or (II):

wherein X₁, X₄, X₅ and X₈ are each independently nitrogen or CR₂; X₂, X₃, X₆ and X₇ are each independently nitrogen or CR₂ when not forming a point of attachment for said repeating unit to adjacent repeating units and are carbon when forming said point of attachment, with the proviso that at least one but no more than two of X₁, X₂, X₃ and X₄ is nitrogen and at least one but no more than two of X₅, X₆, X₇ and X₈ is nitrogen;

R₁ is lower alkenylene, lower alkynylene or a bivalent radical having structure (i):

wherein o is zero or 1, p is zero or 1, q is an integer from 1 to 10, Ar is a nitrogen, oxygen or sulfur-containing heterocyclic moiety, a monocyclic or polycyclic aromatic moiety, any of which moieties may be

unsubstituted or substituted with one or more lower alkyl, lower alkoxyl, cyano or nitro groups; W₁ is lower alkylene, lower alkenylene or lower alkynylene;

each R₂ is independently hydrogen, nitro, cyano, halogen or lower alkyl, lower alkoxy, lower alkaryl, aralkyl, aryl or a nitrogen, oxygen, or sulfur-containing heterocyclic moeity any of which may be unsubstituted or substituted with one or more halogen, lower alkyl, lower alkoxy or aryloxy groups;

W is lower alkylene, lower alkenylene or lower alkynylene; and m is zero or 1, with the proviso that R₁ is other than phenylene, biphenylene or stilbene when said repeating unit has structure (I) where m is zero and q is 1; and R₁ is other than phenylene, biphenylene when said repeating unit has structure (II) and q is 1. In another embodiment, the polymer of the present invention comprises an article of manufacture, such as a thin film, a fiber or a free-standing object, or is comprised in an article of manufacture such as an electronic device, an optoelectronic device or a photonic device. Examples in this last regard include conductors, photoconductors, waveguides, optical switches, light-emitting diodes, such as flexible display devices, electrophotographic and facsimile machines and laser printers.

In still another embodiment, the present invention is directed to a method of solubilizing a polymer of the present invention, as well as polyquinolines, polyanthrazolines and like polymers in general, that involves contact of the same with a complexing agent of a Lewis acid, a dialkyl phosphate, a diaryl phosphate or mixture thereof under conditions effective to cause said polymer to become substantially soluble in a solvent.

In yet another embodiment, the present invention relates to a method for forming an article of manufacture which comprises the aforementioned method of solubilizing to obtain a solution containing the polymer; processing the solution into a desired configuration; and recovering the polymer from the solution under conditions effective to substantially maintain the polymer in the desired configuration.

Figure 1 is a depiction of an embodiment of the method of forming an article of manufacture in accordance with the practice of the present invention. The method depicted relates to the formation of a thin film supported on a frame. Figure 2 is a graph comparing the optical absorption spectra of thin films formed from a known biphenylene-linked polyquinoline, PBQA (Curve 1) to those formed from three thiophene-linked polyquinoline polymers of the present invention, PBTPQ, PBTAPQ and PBTVPQ (Curves 2, 3 and 4).

Figure 3 is a graph comparing the optical absorption spectra of thin films formed from a known biphenylene-linked polyanthrazoline, PBDA (Curve 1) to those formed from three thiophene-linked polymers of the present invention, PBTDA, PBTADA and PBTVDA (Curves 2, 3 and 4).

Figure 4 is a graph comparing the optical absorption spectra of a thin film formed from a known single phenylene-linked polyquinoline, PPPQ (Curve 1) to a thin film formed from a single thiophene-linked polymer of the present invention, PTPQ (Curve 2).

Figure 5 is a graph comparing the optical absorption spectra of a thin film formed from a known single phenylene-linked polyanthrazoline, PPDA (Curve 1) to a thin film formed from a single thiophene-linked polymer of the present invention, PTDA (Curve 2).

Figure 6 is a graph comparing the solution optical absorption spectra, in 0.1 mole % DCP/m-cresol, of a known polyquinoline, PBPQ (Curve 1) and thiophene-linked polymers of the present invention, PBTPQ, PBTAPQ and PBTVPQ (Curves 2, 3 and 4).

Figure 7 is a graph comparing the solution optical absorption spectra, in 0.1 mole % DCP/m-cresol, of a known polyanthrazoline, PBDA (Curve 1) to thiophene- linked polymers of the present invention, PBTDA, PBTADA and PBTVDA (Curves 2, 3 and 4). Figure 8 is a graph comparing the optical absorption spectra of thin films of four polymers of the present invention, PBTPQA (Curve 1), PBTPQA (Curve 2), PBTPQA-OCH₃ (Curve 3) and PBTPQA-F (Curve 4).

Figure 9 is a graph comparing the optical absorption spectra thin films of polymers of the present invention, PBTPQA-OCH₃ (Curve 1), PBTPQA-F (Curve 2) and PBTPQA (Curve 3).

Figure 10 is a graph comparing the solution optical absorption spectra, in 0.1 mo. % of DCP/m-cresol, of two random copolymers of the present invention, PBTPQ/ PBTPQA-OCH₃ (mole ratio 80:20) and PBTPQ/PBTPQA-F (mole ratio 80:20) Curves 1 and 2, respectively.

Figure 11 is a graph comparing the dispersion of the refractive index of thin films formed from two known polyquinolines, PBPQ and PPPQ, to two polymers of the present invention, PBAPQ and PSPQ.

Figure 12 is a graph comparing the dispersion of the refractive index of thin films from three known polyanthrazolines, PBDA, PSPQ and PPDA, to a polymer of the present invention, PBADA and PSDA.

The polymer of the present invention comprises a repeating unit of structure (I) or (II):

wherein X₁, X₄, X₅ and X₈ are each independently nitrogen or CR₂; X₂, X₃, X₆ and X₇ are each independently nitrogen or CR₂ when not forming a point of attachment for said repeating unit to adjacent repeating units and are carbon when forming a point of attachment, with the proviso that at least one but no more than two of X₁, X₂, X₃ and X₄ is nitrogen and at least one but no more than two of X₅, X₆, X₇ and X₈ is nitrogen;

R₁ is lower alkenylene, lower alkynylene or a bivalent radical having structure (i):

wherein o is zero or 1, p is zero or 1, q is an integer from 1 to 10, Ar is a nitrogen, oxygen or sulfur containing heterocyclic moiety, a monocyclic or polycyclic aromatic moiety, any of which moieties may be unsubstituted or substituted with one or more lower alkyl, lower alkoxy, cyano, or nitro groups, W₁ is lower alkylene, lower alkenylene or lower alkynylene;

each R₂ is independently hydrogen, nitro, cyano, halogen or lower alkyl, lower alkoxy, lower alkaryl, aralkyl, aryl or a nitrogen, oxygen or sulfur-containing heterocyclic moiety any of which may be unsubstituted or substituted with one or more halogen, lower alkyl, lower alkoxy or aryloxy groups;

W is lower alkylene, lower alkenylene or lower alkynylene; and m is zero or 1, with the proviso that R₁ is other than phenylene, biphenylene or stilbene when said repeating unit has structure (I), where m is zero, and q is 1; and R₁ is other than phenylene or biphenyl ene when said repeating unit has structure (II) and q is 1.

The substituents in the formula related above and as may be recited elsewhere in this specification unless otherwise indicated are described as follows:

The lower alkyl groups each contain up to 6 carbon atoms which may be in the normal or branched configuration, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, pentyl, hexyl and the like. The preferred alkyl groups contain 1 to 3 carbon atoms; methyl is most preferred.

The lower alkoxy groups each contain up to 6 carbon atoms which may be in the normal or branched configuration, including, for example, methoxy, ethoxy, propoxy and the like. The preferred alkoxy groups contain 1 to 3 carbon atoms; methoxy is most preferred.

The lower alkaryl groups each contain up to 16 carbon atoms, with each alkyl group thereof containing up to 6 carbon atoms, which may be in the normal or branched configuration, and with each aryl group thereof containing from 6 to 10 carbon atoms. Preferably each alkyl group contains 1 to 3 carbon atoms and each aryl group contains 6 carbon atoms.

The aryl groups are aromatic rings containing from 6 to 14 carbon atoms. An aryl group may be a single ring or a combination of multiple rings which may be ortho-fused or joined by one or more single bonds. Examples of the aryl groups include phenyl, α-naphthyl, ß-naphthyl and biphenyl.

T^ne aryloxy groups each contain from 6 to 10 carbon atoms. Preferably, each aryl group contains 6 carbon atoms. The aralkyl groups each contain up to 16 carbon atoms, with each aryl group thereof containing from 6 to 10 carbon atoms and each alkyl group thereof containing up to 6 carbon atoms which may be in the normal or branched configuration. Preferably, each aryl group contains 6 carbon atoms and each alkyl group contains 1 to 3 carbon atoms.

The lower alkenylene groups are bivalent radicals of normal or branched alkenes of 2 to 6 carbon atoms. The lower alkenylene groups may have one carbon-carbon double bond or multiple carbon-carbon double bonds present therein. In configurations having multiple carbon- carbon double bonds, it is preferred that the alkenylene group be in the normal configuration and that the double bonds alternate with carbon-carbon single bonds, i.e, that conjugated double bonds are present. Preferably, the lower alkenylene groups are bivalent radicals of normal alkenes of 2 to 4 carbon atoms wherein a hydrogen from each of the terminal carbon atoms has been removed. Examples of preferred alkenylene groups include vinylene, 1-propenylene, 2-propenylene, butenylene, 2-butenylene and the like. Vinylene is most preferred.

The lower alkynylene groups are bivalent radicals of normal or branched alkynes of 2 to 6 carbon atoms. The lower alkynylene groups may have one carbon-carbon triple bond or multiple carbon-carbon triple bonds. In configurations having multiple carbon-carbon triple bonds, it is preferred that the alkynylene group be in the normal configuration and that the triple bonds alternate with carbon-carbon single bonds. Preferably, the lower alkynylene groups are bivalent radicals of normal alkynes of 2 to 4 carbon atoms wherein a hydrogen from each of the terminal carbon atoms has been removed. A preferred alkynylene group is ethynylene.

As employed herein, the phrase "monocyclic or polycyclic aromatic moiety" includes bivalent radicals formed from an aromatic moiety having up to 12 carbon atoms. It is preferred that the free valencies forming the bivalent aromatic moiety are at ring carbon atoms. A monocyclic or polycyclic aromatic moiety contemplated by the present invention may thus be a monocyclic aromatic ring system, such as a phenylene, or an orthofused polycyclic aromatic ring system, such as a naphthalene, or a polycyclic aromatic ring system joined by one or more single bonds, such as a biphenylene.

As employed herein, the phrase "nitrogen, oxygen or sulfur-containing heterocyclic moiety" includes bivalent radicals formed from heterocyclic rings which include at least one sulfur, nitrogen or oxygen ring atom but which may also include one or several of such atoms. The expression includes bivalent radicals of saturated and unsaturated heterocyclics, as well as heteroaromatic rings, which in the practice of the present invention are preferred. These groups contain 5 to 12 ring atoms in the moiety, which may be formed from a single heterocyclic ring or may be polycyclic, the latter being formed from ortho-fused ring systems or ring systems joined by one or more single bonds. It is preferred that the free valencies of the bivalent moiety are at ring atoms; preferably carbon ring atoms. Representative bivalent radicals in this regard include furylene, pyrrolylene, imidazolylene, pyrazolylene, pyridylene, pyrazinylene and the like. Preferred bivalent radicals are sulfur-containing heterocyclic moi eties, such as thienylene, dithienylene, trithienylene etc; 2,5-thienylene is especially preferred.

Halogens include fluorine, chlorine, bromine, iodine and astatine. Flourine is preferred.

As employed herein, nitro and cyano groups are -NO₂ and -CN, respectively.

In the formula set forth hereinabove, it is preferred, although not necessary, that when R₁ has structure (i), each Ar is the same. Also as indicated in the formula above, either of X₂ or X₃ may form a first point of attachment for said repeating unit to a first adjacent repeating unit and either of X₆ or X₇ may form a second point of attachment for said repeating unit to a second adjacent repeating unit. Generally, the polymer of the present invention is formed of 2 or more repeating units, preferably up to about 600 repeating units (number of repeating units = n; n = 2 to about 600).

In a first embodiment of the polymer of the present invention, X₁ is nitrogen and X₄ is CR₂; X₂ forms a first point of attachment to a first adjacent repeating unit and X₃ is CR₂; X₅ is nitrogen and X₈ is CR₂; X₆ forms a second point of attachment to a second adjacent repeating unit and X₇ is CR₂. It is preferred in this first embodiment that the R₂ associated with X₃ and the R₂ associated with X₇ are each hydrogen, and that the R₂ associated with X₄ is phenyl, and that the R₂ associated with X₈ is phenyl. It is most preferred in this particular arrangement that the repeating unit have structure (I). (This arrangement is referred to hereafter as the "most preferred first embodiment"). In one aspect of this most preferred first embodiment, m is zero.

In a first configuration of this aspect of the most preferred first embodiment, R₁ is an alkenylene having 2 to 4 carbon atoms. The preferred structure of the repeating unit for this configuration, denoted hereinafter as PVPQ, is shown below:

In a second configuration of this aspect of the most preferred first embodiment, R₁ is an alkynylene having 2 to 4 carbon atoms. The preferred structure of the repeating unit for this configuration, denoted herein as PAPQ, is shown below:

In a third configuration of this aspect of the most preferred embodiment, R₁ has structure (i), o, p and q are each 1, W₁ is alkyenlene of 3 to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety. In a preferred practice, W₁ is methylene and each Ar is a phenylene. The structure of the repeating unit in a particularly preferred practice, denoted herein as PDMPQ, is shown below:

In a fourth configuration of this aspect of the most preferred embodiment, R₁ has structure (i), o, p and q are each 1; W₁ is alkynylene having 2 to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety. In a preferred practice, W₁ is ethynylene and each Ar is a phenylene. The structure of the repeating unit in a particularly preferred practice, denoted herein as PBAPQ, is shown below:

In a fifth configuration of this aspect of the most preferred first embodiment, R₁ has structure (i), o and p are each zero, q = 1, and Ar is a bivalent radical of a sulfur-containing heterocyclic moiety, preferably a thienylene. A particularly preferred structure of the repeating unit in this regard, denoted herein as PTPQ, is shown below:

In a variation of this fifth configuration, the thienylene is substituted with one or more alkoxy groups of up to 4 carbon atoms. A preferred alkoxy is methoxy. A particularly preferred structure of the repeating unit in this regard is shown below:

In a sixth configuration of this aspect of the most preferred first embodiment, R₁ has structure (i), o and p are zero, q is 2, and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety; preferably each Ar is a thienylene. A particularly preferred structure of the repeating unit in this regard, denoted herein as PBTPQ, is shown below:

In a variation of this sixth configuration, each thienylene is substituted with one or more alkoxy groups of up to 4 carbon atoms. A preferred alkoxy is methoxy. A particularly preferred structure of the repeating unit in this regard is shown below:

In a seventh configuration of this first aspect, R₁ has structure (i) wherein o and p are each zero; q is 3 and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety; preferably each Ar is a thienylene. A particularly preferred structure in this regard is shown below:

In a eighth configuration of this aspect of the most preferred first embodiment, R₁ has structure (i), o, p and q are each 1, W₁ is an alkenylene of 2 to 4 carbon atoms, and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety. Preferably, W₁ is vinylene in the trans position and each Ar is a thienylene. A particularly preferred structure of the repeating unit in this regard, denoted herein as PBTVPQ, is shown below:

In a ninth configuration of this aspect of the most preferred first embodiment, R₁ has structure (i), o, p and q are each 1, W₁ is an alkynylene of 2 to 4 carbon atoms, and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety. Preferably, W₁ is ethynylene and each Ar is a thienylene. A particularly preferred structure of the repeating unit in this regard, denoted hereinafter as PBTAPQ, is shown below:

In a second embodiment of the polymer of the present invention, X₁ is nitrogen, X₄ is CR₂, X₂ forms a first point of attachment to a first adjacent repeating unit and X₃ is CR₂; preferably the R₂ associated with X₃ is hydrogen and the R₂ associated with X₄ is phenyl. Further in this second embodiment, X₈ is nitrogen and X₅ is CR₂; X₆ is CR₂ and X₇ forms a second point of attachment to a second adjacent repeating unit. Preferably, the R₂ associated with X₅ is phenyl and the R₂ associated with X₆ is hydrogen. It is most preferred in this particular arrangement that the repeating unit have structure (II) (this arrangement is referred to hereafter as the "most preferred second embodiment").

In a first configuration of the most preferred second embodiment, R₁ is an alkenylene of 2 to 4 carbon atoms. In a preferred practice, R₁ is vinylene in the trans position. The structure of the repeating unit having this configuration, denoted herein as PVDA, is shown below:

In a second configuration of the most preferred second embodiment, R₁ is an alkynylene of 2 to 4 carbon atoms. In a preferred practice, R₁ is ethynylene. The structure of the repeating unit having this configuration, denoted hereinafter as PADA, is shown below:

In a third configuration of the most preferred second embodiment, R₁ has structure (i), o, p and q are each 1, W₁ is an alkylene of up to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety. Preferably, W₁ is methylene and each Ar is a phenylene. A particularly preferred structure of the repeating unit in this regard, denoted herein as PDMDA, is shown below:

In a fourth configuration of the most preferred second embodiment, R₁ has structure (i), o, p and q are each 1, W₁ is alkenylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety. Preferably, W₁ is vinylene in the trans position and each Ar is a phenylene. A particularly preferred structure of the repeating unit in this regard, denoted herein as PSDA, is shown below:

In a fifth configuration of the most preferred second embodiment, R₁ has structure (i), o, p and q are each 1, W₁ is alkynylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety. Preferably, W₁ is ethynylene and each Ar is a phenylene. A particularly preferred structure of the repeating unit in this regard, denoted herein as PBADA, is shown below:

In a sixth configuration of the most preferred second embodiment, R₁ has structure (i), o and p are each zero, q is 1 and Ar is a sulfur-containing heterocyclic moiety; preferably Ar is a thienylene. A particularly preferred structure of the repeating unit in this regard, denoted herein as PTDA, is shown below:

In a variation of this sixth configuration, the thienylene is substituted with one or more alkoxy groups of up to 4 carbon atoms. A preferred alkoxy is methoxy. A particularly preferred structure of the repeating unit in this regard is shown below:

In a seventh configuration of the most preferred second embodiment, R₁ has structure (i), o and p are each zero, q is 2 and each Ar is a sulfur-containing heterocyclic moiety; preferably, each Ar is a thienylene. A particularly preferred structure of the repeating unit in this regard, denoted herein as PBTDA, is shown below:

In a variation of this seventh configuration, each thienylene is substituted with one or more alkoxy groups of up to 4 carbon atoms. A preferred alkoxy is methoxy. A particularly preferred structure of the repeating unit in this regard is shown below:

In an eighth configuration of the most preferred second embodiment, R₁ has structure (i), o and p are each zero; q is 3 and each Ar is a sulfur-containing heterocyclic moiety. Preferably, each Ar is a thienylene. A particularly preferred structure of the repeating unit in this regard is shown below:

In a ninth configuration of the most preferred second embodiment, R₁ has structure (i), o, p and q are each 1, W₁ is alkenylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety. Preferably, W₁ is vinylene in the trans position and each Ar is a thienylene. A particularly preferred structure of a repeating unit in this regard, denoted herein as PBTVDA, is shown below:

In a tenth configuration of the most preferred second embodiment, R₁ has structure (i), o, p and q are each 1, W₁ is alkynylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety. Preferably, W₁ is ethynylene and each Ar is a thienylene. A particularly preferred structure of the repeating unit in this regard, denoted herein as PBTADA, is shown below:

In a third embodiment of the polymer of the present invention, the repeating unit has the structure hereinbefore referred to as the most preferred first embodiment; however, in this third embodiment, m is 1. In a first preferred practice of this third embodiment, W is an alkynylene of 2 to 4 carbon atoms.

In a first configuration of this first preferred practice of the third embodiment, R₁ has structure (i), o and p are each zero, q is 2 and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

Preferably, W is ethynylene and each Ar is a thienylene. A particularly preferred structure of the repeating unit in this regard, denoted herein as PBTPQA, is shown below:

In another aspect of this first configuration, the phenyl associated with X₄ is substituted with one or more halogens and the phenyl associated with X₈ is substituted with one or more halogens. A particularly preferred structure of the repeating unit in this regard, denoted herein as PBTPQA-F, is shown below:

In still another aspect of this first configuration, the phenyl associated with X₄ is substituted with one or more alkoxy groups of up to 4 carbon atoms and the phenyl associated with X₈ is substituted with one or more alkoxy groups of up to 4 carbon atoms. Preferably, the alkoxy groups are methoxy. A particularly preferred structure of the repeating unit in this regard, denoted herein as PTBPQA-OCH₃, is shown below:

In a second preferred practice of this third embodiment, N is alkenylene of 2 to 4 carbon atoms. In a first configuration of this second preferred practice of the third embodiment, R₁ has structure (i); o and p are each zero; q is 2 and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety. Preferably, N is vinylene in the trans position and each Ar is a thienylene. A particularly preferred structure of the repeating unit in this regard is shown below:

In another aspect of this first configuration, the phenyl associated with X₄ is substituted with one or more halogens and the phenyl associated with X₈ is substituted with one or more halogens. A particularly preferred structure of the repeating unit in this regard is shown below:

In still another aspect of this first configuration, the phenyl associated with X₄ is substituted with one or more alkoxy groups of up to 4 carbon atoms and the phenyl associated with X₈ is substituted with one or more alkoxy groups of up to 4 carbon atoms. Preferably, the alkoxy groups are methoxy. A particularly preferred structure of the repeating unit in this regard is shown below:

In yet still another aspect of this first configuration, each Ar is a thienylene substituted with one or more alkoxy groups of up to 4 carbon atoms. Preferably, the alkoxy groups are methoxy. A particularly preferred structure of the repeating unit in this regard is shown below:

In a second configuration of this second preferred practice of the third embodiment, R₁ has structure (i); o and p are each zero; q is 1 and Ar is a bivalent radical of a sulfur-containing heterocyclic moiety. Preferably, W is vinylene in the trans position and Ar is a thienylene. A particularly preferred structure of the repeating unit in this regard is shown below:

In a third configuration of this second preferred practice of the third embodiment, W is vinylene in the trans position, R₁ has structure (i); o, p and q are each 1; W₁ is alkynylene of 2 to 4 carbon atoms, and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety. Preferably, W₁ is ethynylene and each Ar is a thienylene. A particularly preferred structure of the repeating unit in this regard is shown below:

In a fourth configuration of this second preferred practice of the third embodiment, W is vinylene in the trans position, R₁ has structure (i); o, p, and q are each 1; W₁ is alkenylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety. Preferably W₁ is vinylene in the trans position and each Ar is a thienylene. A particularly preferred structure of the repeating unit in this regard is shown below:

In a fifth configuration of this second preferred practice of the third embodiment, W is vinylene in the trans position, R₁ has structure (i); o and p are each zero; q is 3; and Ar is a bivalent radical of a sulfur- containing heterocyclic moiety. Preferably Ar is a trithienylene. A particularly preferred structure of the repeating unit in this regard is shown below:

In a fourth embodiment, the polymer of the present invention is a random or block copolymer containing at least one repeating unit contemplated by the present invention. In one aspect of this fourth embodiment, the random copolymer is formed from two or more of the repeating units contemplated by the invention. Thus for example the copolymer comprises a first repeating unit having structure (I) or (II) and a first R₁ and a second repeating unit having structure (I) or (II) and a second R₁ wherein said first R₁ is different from said second R₁, with the remainder of the first repeating unit and the second repeating unit being otherwise the same.

In another aspect of this fourth embodiment, the copolymer is formed by one or more repeating units contemplated by the present invention in combination with known repeating units, such as those which make up the polymers PPQ, PBPQ, PPPQ, PSPQ, PBDA and PPDA. Thus for example in a first configuration of this aspect of the fourth embodiment, the first repeating unit of the random copolymer of the invention is the repeating unit from the polymer PBPQ and the second repeating unit is one contemplated by the present invention, e.g., PBAPQ, as hereinbefore defined.

The structure of this copolymer, denoted herein as PBPQ/PBAPQ, is shown below:

In a second configuration of this aspect of the fourth embodiment of the random copolymer of the present invention, the first repeating unit is one contemplated by the present invention, e.g., PBAPQ, as hereinbefore defined, and the second repeating unit is from the poly mer PSPQ. The structure of this second copolymer, denoted herein PBAPQ/PSPQ, is shown below:

In still another aspect of this fourth embodiment, the copolymer is formed of repeating units contemplated by the invention wherein the R₁ groups are the same but the remainder of the respective repeating units are different. Thus in a first configuration the copolymer comprises a first repeating unit having structure (I) or (II) and a first R₁, and a second repeating unit having structure (I) or (II) and a second R₁ wherein said first R₁ and said second R₁ are the same, with the remainder of the first repeating unit and the second repeating unit otherwise having differences. In an example of this first configuration, the copolymer of the present invention has as a first repeating unit, PBTPQA-F, as hereinbefore defined, and a second repeating unit of PBTPQ, also as hereinbefore defined. The structure of this copolymer, noted herein as PBTPQA- F/PBTPQ, is shown below:

In another example the copolymer has as a first repeating unit, PBTPQA-OCH₃, as hereinbefore defined, and a second repeating unit of PBTPQ, also as hereinbefore defined. The structure of this copolymer, denoted herein as PBTPQA-OCH₃/PBTPQ, is shown below:

In a fifth embodiment the present invention is directed to a random or block copolymer comprising repeating units from known homopolymers, such as those making up PPQ, PPPQ, PSPQ, PBDA, and PPDA. An example of a copolymer contemplated in this regard, denoted PBPQ/PSPQ, is shown below:

The random and block copolymers of the present invention preferably comprise only two repeating units as hereinbefore described and exemplified. The mole ratio of a first repeating unit to a second, different repeating unit in this regard is anywhere from about 0.5:95 to about 95:0.5. Other mole ratios in this regard are about 90:10 to about 10:90; about 80:20 to about 20:80; about 70:30 to about 30:70; about 60:40 to about 40:60 and about 50:50.

In another embodiment, the present invention relates to an article of manufacture comprising a poly mer or copolymer of the present invention, preferably those exemplified hereinabove. Particular articles of manufacture contemplated by this embodiment of the present invention include electronic, optoelectronic and photonic devices, such as filters, optical switches, wave guides, light-emitting diodes, especially flexible display devices and nonlinear optical devices. Other applications for the polymers of the present invention include but are not limited to electrophotographic copying machines, facsimile machines, laser printers and the like. The details pertaining to the inclusion, incorporation and employment of the polymer or copolymer of the present invention into these and similar devices and applications will be readily understood and appreciated by those of skill in the art given the teachings herein.

In another embodiment, the present invention is directed to a method of solubilizing a polymer of the present invention, as well as solubilizing polyquinolines and polyanthrazolines in general, in a solvent. Especially preferred polyquinolines and polyanthrazolines in this last regard are those having a rigid-rod, nonconjugated structure. The term "polymer" as used in regard to the methods of the present invention also includes copolymers as contemplated by the invention or as known heretofore for the class of polyquinolines and polyanthrazolines.

The method of solubilizing of the present invention entails contacting a polymer of the present invention, a polyquinoline, a polyanthrazoline, or mixtures thereof, with a complexing agent of a Lewis acid, a dialkyl phosphate or a diaryl phosphate under conditions effective to cause said polymer (or polymers) to become substantially soluble in said solvent. Lewis acids useful in this regard include those formed from metal halides. Preferred Lewis acids include FeCl₃, SbF₅, SbCl₅, BF₃. Particularly preferred Lewis acids are A1Cl₃ and GaCl₃.

Dialkyl phosphates include those of alkyls having up to 6 carbon atoms; examples include diethyl dithio-phosphate, bis( 2-ethylhexyl) hydrogen phosphate; diaryl phosphates include those of aryls having up to 10 ring carbon atoms. Diphenyl is preferred.

The solvent in which the polymer is solubilized is preferably organic, and is more preferably an aprotic organic solvent. Examples of suitable solvents include nitroalkanes, such as nitromethane, nitroethane and 1-nitropropane. Other solvents include nitrobenzene, dichloromethane, dichloroethane, acetσphene, phenol. Mixtures of these and like solvents may also be employed. Nitroalkanes are preferred.

The conditions effective in the practice of the method of solubilizing contemplated by the present invention generally include a presence of complexing agent in an amount of up to about 20% by weight based said solvent. Preferably, complexing agent is present in an amount of about 15% by weight based on said solvent, more preferably about 10% by weight based on said solvent, and even more preferably about 5% by weight based on said solvent.

The conditions effective in the practice of the method of solubilizing contemplated by the present invention further generally includes a presence of the polymer (or copolymers) to be solubilized in an amount of up to about 3% by weight based on complexing agent plus solvent. Preferably, the polymer is present in an amount of up to about 2%, more preferably about 1% by weight based on complexing agent plus solvent; still more preferably about 0.5 % by weight based on complexing agent plus solvent and yet even more preferably about 0.1% by weight based on complexing agent plus solvent.

Another aspect of the method of solubilizing contemplated by the present invention includes recovering the polymer (or polymers) from the solution thus formed. In the practice of this aspect of the invention, the solvent is removed by techniques known in the art, e.g., evaporation, in an amount sufficient to obtain a remnant which contains the polymer. The remnant is then contacted with a base, preferably one having greater basicity in this regard than the remnant from which the polymer is to be recovered, under conditions effective to obtain the polymer in substantially pure form.

Bases useful in this regard include Lewis bases, preferably those having one or more hydroxy groups. It is preferred that when the polymer has been solubilized using a Lewis acid as a complexing agent that the base be a Lewis base. Examples of Lewis bases especially useful in the practice of this method include water, alkanols of up to six carbon atoms or mixtures thereof. A preferred alcohol is methanol. In a particularly preferred practice of this aspect of the invention, the remnant is washed first with either water or methanol followed by a wash with the other. Other bases useful in this practice of the present invention includes alkylamines in combination with a Lewis base. Alkylamines in this regard are those having up to 6 carbon atoms. It is preferred that when the polymer has been stabilized using a dialkyl phosphate and/or a diaryl phosphate as a complexing agent, that the base be an alkylamine in combination with an

alkanol. Preferably, the alkylamine is triethylemine and the alkanol is ethanol.

In still another embodiment, the present invention is directed to a method of forming an article of manufacture which comprises solubilizing a polymer of the invention, as well as polyquinolines or polyanthrazolines in general, in accordance with the method of solubilizing previously described to obtain a solution containing the polymer. The solution is then processed into a desired configuration and the polymer recovered from the solution under conditions effective to substantially maintain the polymer in the desired configuration.

The polymers of the present invention may be doped to enhance conductivity by techniques known in the art. In particular, the polymers may be p-doped or n- doped. In a preferred practice, the p-doping is with the polymers of the invention wherein R₁ has structure (i) and Ar is a bivalent radical of a nitrogen, oxygen or sulfur-containing heterocyclic moiety, especially a sulfur-containing moiety, and most especially a thienylene.

The following examples are given to illustrate the present invention. These examples are given for illustrative purpose only, and are not intended to limit the present invention.

EXAMPLES

The following materials were prepared or obtained as indicated: The following monomers were prepared as indicated: 3,3'-dibenzoylbenzidine was synthesized as set forth in Macromolecules (1981) 14, 493-502 and

Macromolecules (1990) 23, 2418-2422. 2,5-dibenzoyl-1,4-phenylenediamine was synthesized as set forth in J.

Polym. Sci., Polym. Chem. Ed., (1975) 13, 2233-2249; 5-acetyl-2-amino benzophenone was synthesized as set forth in J. Heterocycl. Chem. (1974) 11 , 107-111; Diacetylstilbene was synthesized as set forth in Macromolecules (1985) 18 , 321-327; 5,5'-Diacetylbiphenylacetylene was synthesized as set forth in Macromolecules (1986) 19, 257-266; Hex-3-ene-2,4-dione was synthesized as set forth in Bull. Soc. Chim. Fr. 1957, 997-1003. Hex-3-yne-2,4-dione was synthesized as set forth in J. Chem. Soc, Perkin Trans. I (1987) 1579-1584; 2,5-diacetylthiophene was synthesized as set forth in J. Org. Chem. (1982) 47, 3027-3038. Di-m-cresyl-phosphate (DCP) was synthesized as set forth in J. Polym. Sci,, Polym.

Symp., 1978, 65, 41-53.

4,4'-diacetyl-1,1'-biphenylene (methanol), 1,4- diacetylbenzene (benzene), and 4,4'-diacetyldiphenylmethane (toluene) were obtained commercially and purified by recrystallization. All other materials were used as obtained: dibenzyl phosphate (Aldrich); diethyl dithiophosphate (Aldrich); bis( 2-ethylhexyl) hydrogen phosphate (Aldrich); diphenyl phosphate (Aldrich);

triphenyl phosphate (Aldrich); AlCl₃ (Aldrich); GaCl₃ (Sigma); triethylamine (Baker). EXAMPLE 1

Preparation of the monomer 1,2-Bis(5-acetyl-2-thienyl)ethylene: To a slurry of 1 g tetrakis(triphenyl phosphine)Palladium (0) in 30 ml of dry toluene was added a solution of 6.6 g (32.2 mmol) of 2-acetyl-5-bromo thiophene in 30 ml of dry toluene under argon.

The light brown solution so obtained was heated to reflux. To this solution was added dropwise a solution of 9.8 g (16.1 mmol) of (E)-1,2-bis(tri-n-butyl stannyl)ethylene, as described in Dokl. Akad. Nauk. SSSR 174, 96, (1967) in 50 ml of toluene (dry) over a period of 1.5 h. After refluxing the reaction mixture for another 5.5 h, it was slowly cooled down to -5°C, and the yellow product was isolated by suction filtration. The product was washed with hexane to remove most of the tri-n-butyltin bromide and dried before it was recrystallized from chloroform. On drying in a vacuum oven at 60°C for 24 hr., a yield of 3.23 g (72.6%) having the following characteristics was obtained, mp 247.6°C; UV/vis λ_max (CHCl₃): 413 (log ε = 4.54), 392 (4.66); FT-IR (KBr, cm- ¹): 3070, 3014, 1655, 1646, 1528, 1459, 1423, 1363, 1276, 1263, 1224, 1075, 1032, 983, 929, 805, 747, 714, 655, 612, 592, 578, 500, 480; ¹H NMR (CD₂Cl₂, 300 MHz, TMS) δ 2.53 (s,6H), 7.15 (d,2H), 7.21 (s,2H), 7.60 (d,2H). Anal. calc. for C₁₄H₁₂S₂: C, 60.84, H, 4.38; N, 0.0. Found: C, 60.55; H, 4.22; N, 0.0.

EXAMPLE 2

Preparation of the monomer 5,5'-Diacetyl-2,2'-bithiophene: To a slurry of 1 g tetrakis(triphenylphosphine) Palladium (0) in 30 ml of dry toluene was added a solution of 6.26 g (30.5 mmol) of 2-acetyl-5-bromo thiophene in 30 ml of dry toluene under argon.

The reaction was heated to reflux and to this solution was added dropwise a solution of 5 g (15.26 mmol) of hexamethylditin (99%) in 50 ml toluene (dry) over a period of 1.5 h. The reaction mixture was refluxed for another 6 h and then cooled down to -5°C. Light yellow crystals of the product were isolated by suction filtration and were washed with hexane. The product was then continuously extracted through Whatman filter paper #42 with dioxane using a soxhlet apparatus until all of the product was dissolved and collected in the boiling flask. Slow cooling of the dioxane solution resulted in needle shaped light yellow crystals of the monomer which were separated by suction filtration and dried in vacuum. A Yield of 2.56 g (67%) having the following characteristics was obtained: mp 235°C (lit. mp 233.5 - 234°C); UV/vis λ_max (CHCl₃): 367 (log ε = 4.19), 262 (3.57); FT-IR (KBr,cm^-1): 3070, 1797 1656, 1611, 1511, 1433, 1361, 1302, 1270, 1089, 1036, 1020, 937, 897, 881, 792, 745, 673, 611, 593, 555, 463, 442; ¹H NMR (CDCl₃ 300 MHz, TMS) δ 2.58 (s,6H), 7.30 (d,2H), 7.62 (d,2H). Anal, calcd. for C₁₂H₁₀S₂: C, 57.58; H, 4.03; N, 0.0. Found: C, 57.48; H, 3.87; N, 0.0.

EXAMPLE 3

Preparation of the monomer 1,2-Bis(5-acetyl-2-thienyl) acetylene: To a slurry of 1 g tetrakis( tri- phenyl phosphine) Palladium (0) in 30 ml of dry toluene was added a solution of 6.6 g (32.2 mmol) of 2-acetyl-5-bromo thiophene in 30 ml of dry toluene under argon.

The light brown solution so obtained was heated to reflux. To this solution was added dropwise a solution of 9.8 g (16.1 mmol) of 1,2-bis(tri-n-butylstannyl)ace¬tylene in 50 ml of toluene (dry) over a period of 2 h. After refluxing the reaction medium for another 6 h, it was cooled down to -5°C, and the yellow product was isolated by suction filtration. The product was washed with hexane to remove most of the tri-n-butyltin bromide. The product was then continuously extracted through Whatman filter paper #42 with dioxane using a soxhlet apparatus until all of the product was dissolved and collected in the boiling flask. Slow cooling of the dioxane solution resulted in needle shaped light yellow crystals of the monomer which were separated by suction filtration and dried in vacuum at 60°C for 24 h. A yield of 2.56 g (65%) having the following characteristics was obtained: mp 214°C; UV/vis λ_max (CHCl₃): 387 (log ε = 4.25), 362 (4.31), 281 (3.78); IR (Nujol, cm- 1): 3070, 1670, 1390, 1295, 1260, 1045, 945, 910, 820; 1H NMR (CD2C12, 300 MHz, TMS) δ 7.60 (d, 2H), 7.33 (d,2H), 2.55 (s,6H).

EXAMPLE 4

Preparation of Poly(2,2'-(p,p'-biphenylacetylene)-6,6'-bis(4-phenylquinoline)) (PBAPQ): Equimolar amounts (3.82 mmol each) of both 3,3'-dibenzoylbenzidine and 5,5'-diacetyl biphenylacetylene were added to a solution of 25 g of di-m-cresyl phosphate (DCP) and 9 g of freshly distilled m-cresol in a cylindrical shaped reaction flask (glass) fitted with a mechanical stirrer, two gas inlets, and a side arm. The reactor was purged with argon for 10-15 min. before the temperature was raised slowly to 140 - 142°C in 2-3 h. As the viscosity of the reaction mixture increased with time, small amounts of m-cresol were added to the reaction mixture to facilitate efficient stirring. The reaction was maintained at this temperature for 48 h under static argon. Thereafter the reaction was quenched by cooling it down to room temperature under argon and precipitating it in 500 ml of 10% triethylamine/ethanol mixture. The precipitated polymer was then chopped in a blender and collected by suction filtration. The polymer was purified by continuous extraction in soxhlet apparatus with 20% triethylamine/ethanol solution for 36 h and was dried in vacuum at 80°C for 24 h. The PBAPQ polymer obtained had the following characteristics: [η] = 8.9 dL/g (25ºC, 0.1 mol% DCP/m-cresol); FT-IR (freestanding film, cm^-1): 3057, 3036, 1586, 1575, 1538, 1519, 1488, 1455, 1410, 1358, 1234, 1181, 1153, 1110, 1065, 1016, 874, 840, 828, 786, 771, 735, 701, 622, 588; Anal, calcd. for (C₄₄H₂₆N₂) _n : C, 90.70; H, 4.50; N, 4.84. Found: C, 88.87; H, 4.49; N, 4.69. EXAMPLE 5

Preparation of Poly(2,2'-(4,4'-diphenylmethane)-6,6'-bis(4-phenylquinoline)) (PDMPQ): PDMPQ was synthesized using the procedure described in Example 4 using equimolar amounts (1.78 mmol each) of 3,3'-dibenzoylbenzidine (18) and diacetyldiphenylmethane as the two monomers. 15 g of diphenyl phosphate with 8 g of m-cresol was used as the reaction medium instead of DCP/m-cresol. The PDMPQ polymer obtained had the following characteristics: [η] = 9.3 dL/g (25°C, 0.1 mol% DCP/m-cresol); FT-IR (freestanding film, cm^-1): 3056, 3028, 1585, 1572, 1541, 1486, 1427, 1353, 1230, 1182, 1152, 1065, 1017, 910, 826, 761, 700, 587; Anal, calcd. for (C₄₃H₃₃N₂)_n: C, 90.18; H, 4.93; N, 4.89. Found: C, 85,34; H, 4.51; N, 4.58.

EXAMPLE 6

Preparation of Poly(2,7-(p,p'-biphenylacetylene)-4,9-diphenyl-1,6-anthrazoline) (PBADA): PBADA was synthesized and isolated according to the procedure described in Example 4 using equimolar amounts (2.21 mmol each) of the monomers 2,5-dibenzoyl-1,4-phenylenediamine and diacetylbiphenylacetylene as reactants which were added to a mixture of 15 g of DCP and 8 g of m-cresol. The PBADA polymer obtained had the following characteristics: [η] = 7.65 dL/g (25°C, 0.1 mol% DCP/m-cresol); FT-IR (freestanding film, cm^-1): 3037, 2967, 1590, 1558, 1519, 1492, 1453, 1408, 1351, 1288, 1238, 1181, 1052, 1016, 970, 894, 840, 765, 699, 539; Anal, calcd. for (C₃₈H₂₂N₂)_n: C, 90.09; H, 4.38; N, 5.53. Found: C, 86.92; H, 4.20; N, 5.23.

EXAMPLE 7

Preparation of Poly(2,7-(p,p'-stilbene)-4,9-diphenyl-1,6-anthrazoline) (PSDA): PSDA was synthesized and isolated according to the procedure described in Example 6 using equimolar amounts (2.21 mmol each) of 2,5-dibenzoyl-1,4-phenylenediamine and diacetylstilbene as reactants. The PSDA polymer obtained had the following characteristics: [η] = 30.3 dL/g (25°C, 0.1 mol % DCP/m-cresol); FT-IR (freestanding film, cm^-1): 3028, 2966, 1733, 1590, 1572, 1492, 1453, 1415, 1349 1238, 1181, 1148, 1053, 1015, 969, 894, 840, 765, 699, 533; Anal, calcd. for (C₃₈H₂₄N₂) _n: C, 89.74; H, 4.76; N, 5.51. Found: C, 85.66; H, 4.55; N, 5.32.

EXAMPLE 8

Preparation of Poly(2,7-(4,4'-diphenylmethane)-4,9-diphenyl-1,6-anthrazoline) (PDMDA): PDMDA was synthesized and isolated according to the procedure described in Example 4 using equimolar amounts (2.21 mmol each) of 2,5-dibenzoyl-1,4-phenylenediamine and diacetyldiphenylmethane as reactants in a reaction medium of 15 g DPP and 11.5 g m-cresol. The polymer obtained was worked up as usual. The PDMDA polymer obtained had the following characteristics: [η] = 0.87 dL/g (25°C, 0.1 mol% DCP/m-cresol); FT-IR (freestanding film, cm^-1): 3027, 1588, 1566, 1528, 1510, 1490, 1451, 1433, 1412, 1363, 1344, 1276, 1234, 1180, 1147, 1110, 1074, 1051, 1030, 1016, 969, 893, 816, 761, 697; Anal. calcd. for (C₃₇H₂₄N₂)_n: C, 89.49; H, 4.87; N, 5.64. Found: C, 87.34; H, 4.68; N, 5.40.

EXAMPLE 9

Preparation of Poly(2,2'-(2,2'-bithiophenyl)-6,6'-bis(4-phenylquinoline)) (PBTPQ): PBTPQ was synthesized isolated according to the procedure described in Example 4 using equimolar amounts (1.27 mmol each) of 3,3'-dibenzoylbenzidine and 5,5'-diacetyl-2,2'-bithiophene prepared according to the procedure described in Example 2, as reactants which were mixed with 12 g DCP and 2 g m-cresol. The PBTPQ polymer obtained had the following characteristics: [η] = 11.5 dL/g (25ºC, 0.1 mol % DCP/m-cresol); FT-IR (freestanding film, cm^-1): 3063, 2967, 1586, 1543, 1519, 1489, 1454, 1442, 1360, 1282, 1225, 1076, 871, 823, 787, 767, 701, 621, 590; anal, calcd. for (C₃₈H₂₂N₂S₂)_n: C, 79.97; H, 3.89; N, 4.91. Found: C, 78.27; H, 3.89; N, 4.77.

EXAMPLE 10

Preparation of Poly(2,2'-(2-thienylethynyl-2-thienyl)-6,6'-bis(4-phenylquinoline)) (PBTAPQ): PBTAPQ was synthesized and isolated according to the procedure described in Example 4 using equimolar amounts (1.27 mmol each) of 3,3'-dibenzoylbenzidine and 1,2-Bis(5-acetyl-2-thienyl)acetylene prepared according to the procedure described in Example 3 were mixed with 12 g DCP and 2 g m-cresol. The PBTAPQ polymer obtained had the following characteristics: FT-IR (freestanding film, cm^-1): 3059, 2969, 1740, 1590, 1544, 1489, 1465, 1359, 1304, 1243, 1149, 1069, 1030, 970, 874, 825, 768, 701, 585; Anal, calcd. for (C₄₀H₂₂N₂S₂)_n: C, 80.78; H, 3.73; N, 4.71. Found: C, 77.04; H, 4.12; N, 4.13. Intrinsic viscosity was not determined.

EXAMPLE 11

Preparation of Poly(2,2'-(2-thienylethenyl-2- thienyl)-6,6'-bis(4-phenylquinoline)) (PBTVPQ): PBTVPQ was synthesized and isolated according to the procedure described in Example 4 using equimolar amounts (1.27 mmol each) of 3,3'-dibenzoylbenzidine and 1,2-Bis(5- acetyl-2-thienyl)ethylene prepared according to the procedure described in Example 1, as reactants which were mixed with 12 g DCP and 2 g m-cresol. The polymer PBTVPQ obtained had the following characteristics: [η] = 6.2 dL/g (25°C, 0.1 mol% DCP/m-cresol); FT-IR (free- standing film, cm^-1): 3060, 2968, 1586, 1545, 1473, 1360, 1259, 1238, 1066, 1029, 932, 874, 825, 768, 701, 621, 586; Anal, calcd. for (C₄₀H₂₄N₂S₂)_n: C, 80.51; H,

154.05; N, 4.69. Found: C, 78.02; H, 4.22; N, 4.71.

EXAMPLE 12

Preparation of Poly(2,2'-(2,5-thiophenyl)-6,6'-bis(4-phenylquinoline)) (PTPQ): PTPQ was synthesized and isolated according to the procedure described in Example 4 using equimolar amounts (1.78 mmol each) of 3,3'-dibenzoylbenzidine and 2.5-diacetyl thiophene as reactants in 16.5 g DCP and 2 g m-cresol. The PTPQ polymer obtained had the following characteristics: [η] = 10.5 dL/g (25°C, 0.1 mol% DCP/m-cresol); FT-IR (free-standing film, cm^-1): 3057, 2967, 1586, 1544, 1489, 1451, 1362, 1235, 1150, 1075, 1030, 872, 846, 824, 767, 701, 623, 570; Anal, calcd. for (C₃₄H₂₀N₂S₁)_n: C, 83.58; H, 4.13; N, 5.73. Found: C, 81.31; H, 4.02; N, 5.55.

EXAMPLE 13

Preparation of Poly(2,7-(2,2'-bithiophenyl)-4,9-diphenyl-1,6-anthrazoline) (PBTDA): Equimolar amounts of both 2,5-dibenzoyl-1,4-phenylenediamine (0.5 g) and 5,5'-diacetyl-2,2'-bithiophene (0.3957 g), prepared according to the procedure described in Example 2, were added along with 15 g of diphenyl phosphate (DPP) and 2 g of freshly distilled m-cresol in a glass reactor fitted with mechanical stirrer, two gas inlets, and a side arm. The reaction mixture was purged with argon for 15 min., and then the temperature was slowly raised in steps to 140°C under positive pressure of argon. The temperature was maintained for 48 h, during which time small amounts of m-cresol were added to facilitate efficient stirring of the reaction mixture whenever it became highly viscous. After cooling, the polymerization dope was slowly poured into the stirred solution of 55 mL of ethanol/500 mL of triethylamine (TEA). The precipitated polymer was then chopped in a blender and collected by suction filtration. The polymer was purified by continuously extracting it with 20% TEA/ethanol solution for 24-36 h and was dried in vacuum at 80°C. The PBTDA obtained had the following characteristics: [η] = 2.3 dL/g (25°C 1.5 mol % DCP/m-cresol); IR (free- standing film, cm^-1) 3055, 2964, 1588, 1527, 1492, 1442, 1425, 1358, 1274, 1232, 1074, 1030, 892, 794, 765, 700, 613, 549. Anal. Calcd. for (C₃₂H₁₈N₂S₂)_n: C, 77.7; H, 3.67; N, 5.66. Found: C, 75.76; H, 3.59; N, 5.34.

EXAMPLE 14

Preparation of Poly(2,7-(2,2'-thienylethynyl-2-thienyl)-4,9-diphenyl-l,6-anthrazoline) (PBTADA):

PBTADA polymer was prepared using equimolar amounts of 2,5-dibenzoyl-1,4-phenylenediamine (0.5 g) and 1,2-bis(5-acetyl-2-thienyl) acetylene (0.4336 g), prepared according to the procedure described in Example 3 in di-m-cresyl phosphate (DCP) as the solvent medium instead of DPP. The same procedure as described in Example 13 was used for the polymerization. The PBTADA polymer obtained had the following characteristics: [η] = 4.4 dL/g (25°C, 0.1 mol % DCP/m-cresol); IR (free-standing film, cm^-1) 3055, 2971, 1589, 1530, 1492, 1445, 1427, 1355, 1290, 1240, 1063, 1030, 894, 807, 766, 701, 614, 546. Anal. Calcd. for (C₃₄H₁₈N₂S₂)_n: C, 78.74; H, 3.50; N, 5.40. Found: C, 76.82; H, 4.03; N, 4.66.

EXAMPLE 15

Preparation of Poly(2,7-(2,2'-thienylethenyl-2-thienyl)-4,9-diphenyl-1,6-anthrazoline) (PBTVDA):

PBTVDA was synthesized and isolated according to the procedure described in Example 13 using equimolar amounts (1.58 mmol each) of 2,5-dibenzoyl-l,4-phenylenediamine and 1,2-Bis(5-acetyl-2-thienyl)ethylene prepared according to the procedure described in Example 1, as reactants which were reacted in 12 g DCP and 2.5 g m-cresol. The PBTVDA polymer obtained had the following characteristics: [η] = 4.4 dL/g (25°C, 0.1 mol% DCP/m-cresol); IR (freestanding film, cm^-1): 3060, 2968, 1588, 1574, 1532, 1492, 1475, 1357, 1289, 1259, 1239, 1146, 1061, 1030, 959, 934, 895, 796, 765, 748, 702, 616, 545; Anal, calcd. for (C₃₄H₂₀N₂S₂)_n: C, 78.43; H, 3.87; N, 5.38. Found: C, 77.38; H, 3.83; N, 5.09.

EXAMPLE 16

Preparation of Poly(2,7-(2,5-thiopheneyl)-4,9- diphenyl-1,6-anthrazoline) (PTDA): PTDA was synthesized and isolated according to the procedure described in Example 15 using equimolar amounts (1.58 mmol each) of 2,5-dibenzoyl-1,4-phenylenediamine and 2,5-diacetylthiophene as reactants. The PTDA polymer obtained had the following characteristics: [η] = 1.2 dL/g (25°C, 0.1 mol% DCP/m-cresol); FT-IR (freestanding film, cm^-1): 103056, 3028, 1586, 1571, 1529, 1491, 1432, 1354, 1234, 1042, 1030, 892, 851, 805, 763, 698, 616, 587; Anal, calcd. for (C₂₈H₁₆N₂S₁)_n: C, 81.53; H, 3.91; N, 6.79. Found: C, 78.68; H, 3.83; N, 6.29

EXAMPLE 17

Preparation of the copolymer PBPQ/PBAPQ: 1.27 mmoles of 4,4'-diacetyl-1,1'-biphenylene; 1.27 mmoles of 5,5'-diacetylbiphenylacetylene, and 2.55 mmole of 3, 3'-dibenzoylbenzidine were mixed together in a reaction medium of 17 g DCP and 16 g/m-cresol. Synthesis and isolation of the copolymer was carried out as described in Example 4. The copolymer obtained had the following characteristics: [η] = 25 dL/g (25°C, 0.1 mol % DCP/m-cresol); FT-IR (freestanding film, cm^-1): 3057, 3033, 2960, 1586, 1539, 1488, 1457, 1357, 1233, 1151, 1154, 1068, 1016, 1004, 872, 827, 771, 701, 623, 590.

EXAMPLE 18

Preparation of the copolymer PBAPQ/PSPQ: 1.27 mmoles of 4,4'-diacetylstilbene, 1.27 mmoles of 5,5'-diacetylbiphenylacetylene, and 2.55 mmole of 3,3'-dibenzoylbenzidine were mixed together in a reaction medium of 17 g DPP and 15 g m-cresol. Synthesis and isolation of the copolymer was carried out as described in Example 4. The copolymer obtained had the following characteristics: [η] = 14.3 dL/g (25°C, 0.1 mol% DCP/m-cresol); FT-IR (freestanding film, cm^-1): 3057, 3030, 2960, 1586, 1575, 1539, 1488, 1460, 1357, 1235, 1181, 1065, 1015, 828, 771, 701, 588.

EXAMPLE 19

Preparation of the copolymer PSPQ/PBPQ: 1.27 mmole of 4,4'-diacetylstilbene, 1.27 mmole of diacetyl- 1,1'-biphenylene and 2.55 mmol of 3,3'-dibenzoylbenzidine were mixed together in a reaction medium of 17 g DCP and 16 g m-cresol. The reaction was carried out as described in Example 4. The polymer obtained was worked up as usual. [η] = 22.6 dL/g (25°C, 0.1 mol% DCP/m- cresol); FT-IR (freestanding film, cm^-1): 3057, 3029, 102960, 1586, 1574, 1540, 1488, 1457, 1357, 1234, 1182, 1068, 1004, 870, 827, 772, 743, 701, 590.

EXAMPLE 20

Preparation of 5-Bromo-2-(trifluoroacetamido) benzophenone (hereafter "Compound 1"): To a solution of 17 g (61.6 mmol) of 2-amino-5-bromo benzophenone in 556 ml of diethyl ether (anhydrous) was added 64.3 g (0.61 mol) of anhydrous sodium carbonate. The mixture was cooled in an ice-bath and trifluoro acetic anhydride was added dropwise as rapidly as possible to maintain at the most a gentle reflux. The reaction mixture was removed from the ice-bath and stirred for 30 min. at room temperature. The white slurry was separated between 700 ml of water and 700 ml of methylene chloride. After removing the aqueous phase, the organic phase was washed twice with water and dried over MgSO₄. Removal of the solvent gas 22.3 g (97.4% yield) of off-white solid, mp °C; ¹H NMR (CDCl₃, 300 MHz) d: 7.54 - 7.59 (m,2H), 7.66 - 7.80 (m,5H), 8.55 (d,1H), 11.89 (br. s, 1H).

EXAMPLE 21

Preparation of 1,2-Bis(trifluoroacetamido)-3,3'-dibenzoyldiphenyl-1-1'-acetylene (hereafter "Compound 2"): To a mixture of 22 g (59.1 mmol) of Compound 1 in 220 ml of dry toluene was added a mixture of 1 g of tetrakis(triphenyl phosphine)Palladium(0) in 50 ml of dry toluene under argon. The light brown solution so obtained was heated to reflux and to this solution was added dropwise a solution of 17.9 g (29.6 mmol) of bis(tri-n-butylstannyl)acetylene in 92 ml of dry toluene. On completion of the addition, the reaction was refluxed for an additional 10 h. The reaction was cooled to -5°C and yellow product isolated was by suction filtration followed by drying. Crude yield 14.5 g (80%). The product was purified by recrystallization from 300 ml of tetrahydrofuran. Yield 13.2 g (73%). mp 253.8°C; ¹H NMR (CDCl₃, 300 MHz) d: 7.53 - 7.58 (m,4H), 7.66 - 7.81 (m,10H), 8.65 (d,2H), 12.04 (br,s,2H); Anal, calcd. for C₃₂H₁₈N₂O₄F₆: C, 63.16; H, 2.98; N, 4.60. Found: C, 62.84; H, 2.79; N, 4.55.

EXAMPLE 22

Preparation of 4,4'-Diamino-3,3'-dibenzoyldi¬phenyl-1,1'-acetylene (hereafter "Compound 3"): A mixture of 13 g (21.4 mmol) of Compound 2, 425 ml of de- gassed ethanol, 105.3 ml of water and 19.15 g (0.181 mol) of anhydrous sodium carbonate was refluxed for 72 h. The yellow slurry was cooled to room temperature, and the product was separated by filtration. After washing the product twice with water and then with a little methanol, it was dried in vacuum at 70°C for 24 h. Crude yield 8.66 g (97.3%). The product was purified by continuously extracting it in dioxane using a soxhlet apparatus (with a double thickness thimble lined with Whatman # 42 filter paper) until all of the product was dissolved and recrystallized in the boiling flask. The pure product was recovered by suction filtration, washed with hexane and methanol and dried in vacuum at 60°C for 24 h. Yield 7.5 g (84%). mp 310.1°C; FT-IR (KBr,cm-¹): 3457, 3338, 1630, 1619, 1578, 1545, 1488, 1445, 1417, 1381, 1326, 1306, 1290, 1245, 1170, 1135, 975, 911, 880, 831, 807, 758, 712, 706, 659, 552; Anal, calcd. for C₂₈H₂₀N₂O₂: C, 80.75; H, 4.84; N, 6.73.

Found: C, 80.53; H, 4.71; N, 6.46.

EXAMPLE 23

Preparation of 3-(p-methoxyphenyl)-5-bromo-2,1-benzisoxazole (hereafter "Compound 4"): To a solution of 148 g of potassium hydroxide in 300 ml of anhydrous methanol at 0°C was added 21.3 g (0.145 mole) of 4-methoxy phenylacetonitrile. The mixture was stirred at 0°C for 10 min. and then a solution of 25.4 g (0.126 mol) of p-bromo nitrobenzene in 300 ml of tetrahydrofuran and methanol (1:2) was slowly added over a period of 1 h. The deep purple mixture was continuously stirred and maintained at 0 - 5°C during addition. The temperature was then raised to 55°C using a hot water bath and reaction mixture was stirred for another 3 h. On cooling, the reaction mixture was poured into 1500 ml of water, and the brown precipitate was separated by suction filtration. The product was washed twice with water followed by cold methanol. The yellow solid so obtained was recrystallized twice from methanol to give needle like light yellow crystals. Yield 19.5 g (51%). mp 137.1°C. Anal. calcd. for C₁₄H₁₀NO₂Br: c, 55.29; H, 3.31; N, 4.61. Found: C, 54.99; H, 3.14; N, 4.62

EXAMPLE 24

Preparation of 2-Amino-5-bromo-4'-methoxy benzophenone (hereafter "Compound 5"): To a solution of 19.3 g of Compound 4 in 193 ml of acetic acid (glacial) at 95°C was added 28.95 g of iron filings and 63 ml of water in 12 equal portions over a period of 3 h. The reaction was allowed to run for an additional 20 minutes after which it was cooled down to room temperature.

This step gave a green slurry which was diluted with 1500 ml of water. Yellow product was extracted from this mixture in ethyl ether which was then washed with sodium carbonate solution followed by water and dried over MgSO₄. Removal of solvent gave yellow solid as the product which was recrystallized from methanol to give a yield of 16.6 g (85.4%). mp 120.4°C; ¹H NMR (CDCl₃, 300 MHz) d: 3.9 (s,3H), 5.87 (br. s, 2H), 6.64 (d,1H); 6.96 (d,2H), 7.32 - 7.4 (m,1H), 7.57 (d,1H), 7.65 - 7.75 (d,2H); Anal, calcd. for C₁₄H₁₂NO₂Br: C, 54.92; H, 3.95; N, 4.57. Found: C, 54.70; H, 3.74; N, 4.56.

EXAMPLE 25

Preparation of 5-Bromo-4'-methoxy-2-(trifluoro¬acetamido) benzophenone (hereafter "Compound 6"): To a solution of 16 g (52.3 mmol) of Compound 5 in 368 g of ethyl ether (dry) was added 54 g (0.515 mol) of sodium carbonate (anhydrous). The slurry was cooled in an ice bath and 37.2 ml (0.263 mol) of trifluoroacetic anhydride was added dropwise as rapidly as possible to maintain at the most a gentle reflux. Thick white slurry so obtained, was stirred at room temperature for another 45 minutes and then separated between 500 ml of methylene chloride and 500 ml of water. The aqueous layer was removed and organic layer was washed twice with water before drying it over MgSO₄. Removal of solvent gave 21.02 g (95.5%) of off-white product, mp 148.9°C; ¹H NMR (CDCl₃, 300 MHz) d: 3.93 (s,3H), 7.02 (d,2H), 7.75 - 7.78 (m, 4H), 8.49 (d,1H), 11.66 (br. s,1H); Anal, calcd. for C₁₆H₁₁NO₃BrF₃: C, 47.79; H, 2.76; N, 3.48. Found: C, 47.67; H, 2.70; N, 3.51.

EXAMPLE 26

Preparation of 4-4'-Bis(trifluoroacetamido)-3-3'-di-p-methoxybenzoyldiphenyl;-1,1'-acetylene (hereafter "Compound 7"): To a solution of 19.5 g of Compound 6 in 233 ml of dry toluene was added a mixture of 1 g of tetrakis(triphenyl phosphine)Palladium (0) and 50 ml of dry toluene under argon. The mixture was heated to reflux, and to it was added dropwise a solution of 14.6 g (24.2 mmol) of bis (tri-n-butyl stannyl) acetylene in 76.5 ml of dry toluene over a period of 2 h. The reaction was refluxed for an addition 10 h during which time part of orangish-yellow product precipitated. After cooling the reaction mixture to -5°C, the product was isolated by suction filtration (crude yield 13.03 g, 80%). The product was purified by continuously extracting it in toluene using soxhlet apparatus (with double thickness thimble lined with Whatman # 42 filter paper) until all of the product was dissolved and collected in the boiling flask. The pure product was recovered by suction filtration of the cold toluene mixture (at - 5°C). Yield 11 g (68%). mp 261.2°C; ¹H NMR (CDCl₃, 300 MHz) d: 3.93 (s,6H), 7.02 (d,4H), 7.75 - 7.80 (m,8H), 8.60 (d,2H), 11.82 (br. s, 2H); Anal, calcd. for

C₃₄H₂₂N₂O₆F₆: C, 61.08; H, 3.32; N, 4.19. Found C, 60.80; H, 3.20; N, 4.19.

EXAMPLE 27

Preparation of 4,4'-Diamino-3,3'-di-p-methoxybenzoyldipheny1-1,1'-acetylene (hereafter "Compound 8"): 11 g of Compound 7 was mixed with 350 ml of degassed ethanol, 89 ml of water, and 15 g (0.142 mol) of sodium carbonate. The mixture was refluxed for 84 h. Bright yellow slurry was cooled to room temperature, filtered and the solid product dried to give crude yield of 7.7 g. The product was purified by continuously extracting it in dioxane using soxhlet apparatus (with double thickness thimble line with Whatman # 42 filter paper) until all of the product was dissolved and recrystallized in the boiling flask. Pure product was recovered by suction filtration and dried in vacuum at 60°C for 24 h. Yield was 6.3 g (80%). mp 235.3°C; ¹H NMR (CDCl₃, 300 MHz) d: FT-IR (KBr, cm-¹): 3457, 3345, 1624, 1602, 1562, 1570, 1508, 1461, 1441, 1415, 1363, 1305, 1258, 1243, 1172, 1111, 1028, 977, 957, 881, 843, 785, 695, 635, 614; Anal, calcd. for C₃₀H₂₄N₂O₄: C, 75.62; H, 5.08; N, 5.88. Found: C, 75.86; H, 5.01; N, 5.78

EXAMPLE 28

Preparation of 5-Bromo-2'-fluoro-2-(trifluoroacetamido)benzophenone (hereafter "Compound 9"): To a solution of 12 g of 2 amino-5-bromo-2'-fluoro benzophenone (Lancaster) in 407 ml of dry diethylether was added 42.6 g of anhydrous sodium carbonate. The reaction mixture was cooled in an ice bath, and 29 ml of trifluoroacetic anhydride was added dropwise as rapidly as possible while maintaining at the most a gentle reflux. Thereafter, the ice bath was removed, and the reaction mixture was stirred for 30 min. at room temperature.

The off-white reaction slurry was separated between 500 ml methylene chloride and 500 ml of water. The aqueous layer was removed and organic layer was washed twice with water and dried over MgSO₄. Filtration and evaporation of the solvent gave 15.7 g (98.5%) of product, mp 132°C; ¹H NMR (CDCl₃, 300 MHz) d: 7.24 (t,1H), 7.35 (t,1H), 7.50 - 7.55 (m,1H), 7.60 - 7.67 (m,1H), 7.72 (t,1H), 7.77 - 7.81 (d of d,1H), 8.62 (d,1H), 12.29 (s,1 NH); Anal, calcd. for C₁₅H₈NO₂BrF₄: C, 46.18; H, 2.07; N, 3.59. Found: C, 46.33; H, 1.94; N, 3.68.

EXAMPLE 29

Preparation of 4,4'-Bis(trifluoroacetamido)-3-3'-di-o-fluorobenzoyldiphenyl-1,1'-acetylene (hereafter "Compound 10"): To a solution of 15 g (38.4 mmol) of Compound 9 in 100 ml of dry toluene was added a mixture of 1 g of tetrakis (triphenylphosphine)Palladium (0) in 50 ml of dry toluene under argon. The reaction mixture was then heated to reflux, and to this mixture was added dropwise a solution of 11.6 g (19.2 mmol) of bis(tri-n-butylstannyl) acetylene in 60 ml toluene (dry) over a period of 2 h. The reaction was refluxed for an additional 10 hrs after which it was cooled down to -5°C. The yellow crystals of product were isolated by suction filtration followed by washing with hexane. The crude product obtained (12.4 g) was dissolved in excess chloroform, filtered and then recrystallized from chloroform to give a yield of 7.6 g (61.1%). mp 267.2°C; ¹H NMR (CDCl₃, 300 MHz) d: 7.24 (t,2H), 7.35 (t,2H), 7.5 - 7.55 (m,2H), 7.59 - 7.67 (m,2H), 7.72 (t,2H), 7.76 - 7.81 (d of d,2H), 8.71 (d,2H), 12.29 (s,2NH); Anal, calcd. for C₃₂H₁₆N₂O₄F₈: C, 59.64; H, 2.50; N, 4.35. Found: C, 59.24; H, 2.41; N, 4.33.

EXAMPLE 30

Preparation of 4,4'-Diamino-3,3'-di-o-fluorodibenzoyldiphenyl-1,1'-acetylene (her(after "Compound 11"): A mixture of 7.35 g (11.5 mmol) of Compound 10, 10.36 g (98 mmol) of anhydrous sodium carbonate, 57 ml of water and 230 ml of degassed ethanol was heated at reflux for 72 h. On cooling, the solid product was separated by suction filtration, washed with water

(twice), and dried in vacuum oven. Crude yield 5.05 g. The product was purified by continuously extracting it in chloroform using soxhlet apparatus (with double thickness thimble layered with Whatman # 42 filter paper) until all of the product was dissolved and recrystallized in the boiling flask. Upon cooling, the product was isolated by suction filtration and dried in vacuum oven at 60°C for overnight. Yield was 4.24 g (82%). Compound 11 did not show any mp, exothermic peak (possibly crosslinking) starts around 290°C; FT-IR (KBr, cm^-1): 3464, 3338, 1638, 1621, 1582, 1545, 1485, 1450, 1420, 1364, 1329, 1307, 1289, 1270, 1245, 1218, 1172, 1138, 976, 887, 830, 817, 757, 648; Anal, calcd. for C₂₈H₁₈N₂O₂F₂: C, 74.33; H, 4.01; N, 6.19; F, 8.40.

Found C, 73.98; H, 3.93; N, 6.12; F, 8.46.

EXAMPLE 31

Preparation of the polymer Poly(2,2'-(2,2'-bithiophene)-6,6'-bis(4-phenylquinoline)acetylene

(PBTPQA): Equimolar amounts (1.2 mmol each) of both 4,4'-diamino-3,3'-dibenzoyldiphenyl-1,1'-acetylene

(Compound 3) and 5,5'-diacetyl-2,2'-bithiophene were added to a solution of 12 g of di-m-cresyl phosphate (DCP) and 15 g of freshly distilled m-cresol in a cylindrical shaped reaction flask (glass) fitted with a mechanical stirrer, two gas inlets, and a side arm. The reactor was purged with argon for 10 - 15 min. before the temperature was raised slowly to 90°C. The reaction was run at this temperature for 24 h and then at 120 - 130°C for an additional 10 h under static argon. There-after the reaction was quenched by cooling it down to room temperature under argon and precipitating it in 500 ml of 10% triethylamine/ethanol mixture. The precipitated polymer was then collected by suction filtration. The polymer was purified by continuous extraction in soxhlet apparatus with 20% triethylamine/ethanol solution for 36 h and was dried in vacuum at 80°C for 24 h. The PBTPQA polymer obtained had the following characteristics: [η] = 0.89 dL/g (25°C,0.5 mol % DCP/m-cresol); FT-IR (KBr,cm^-1): 3050, 2910, 1584, 1542, 1490, 1457, 1438, 1361, 1290, 1229 (w), 1155, 1074, 1030, 873, 835, 797, 767, 700, 619, 584; Anal, calcd. for (C₄₀H₂₂N₂S₂)_n: C, 80.78; H, 3.73; N, 4.71. Found: C, 77.5; H, 4.32; N, 3.96. EXAMPLE 32

Preparation of the polymer Poly(2,2'-(2,2'-bithiophene)-6,6'-bis(4-(p-methoxy)phenylquinoline acetylene) ( PBTPQA-OCH₃): Equimolar amounts (1.2 mmol each) of both 4,4'-diamino-3,3'-di-p-methoxybenzoyldiphenyl-1,1'-acetylene (Compound 8) and 5,5'-diacetyl-2,2'-bithiophene were added to a solution of 12 g of di-m-cresyl phosphate (DCP) and 15 g of freshly distilled m-cresol in a reaction flask as described in Example 31. The reaction was purged with argon for 10 - 15 min.

before the temperature was raised slowly to 60°C and then to 90°C. The reaction was run at 90°C for 4 h and then at 100°C for addition 15 h under static argon. The temperature was then raised to 125 - 130°C for 5 h and then to 140°C for 2 h. As the viscosity of the reaction mixture increased with time, addition at m-cresol was added to the reaction mixture to maintain diluted conditions. Thereafter the reaction was quenched, precipitated, and purified as described in Example 31. The PBTPQA-OCH₃ polymer obtained had the following characteristics: [η] = 1.1 dL/g (25°C, 0.5 mol 5 DCP/m-cresol); FT-IR (KBr,cm-¹): 3055, 2914, 1649, 1608, 1583, 1541, 1511, 1453, 1439, 1400, 1362, 1291, 1248, 1176, 1031, 832, 798, 573; Anal, calcd. for (C₄₂H₂₆N₂O₂S₂)n: C, 77.04; H, 4.00; N, 4.28. Found: C, 74.27; H, 4.51; N, 3.60.

EXAMPLE 33

Preparation of the polymer Poly(2,2'-(2,2'-bithiophene)-6,6'-bis(4-(o-fluoro)phenylquinoline acetylene) ( PBTPAQA-F): Equimolar amounts (0.663 mmol each) of both 4,4'-diamino-3,3'-di-o-fluαrodibenzoyldiphenyl-1,1'-acetylene (Compound 11) and 5,5'-diacetyl-2,2'-bithiophene were reacted as described in Example 31.

The polymer product was collected and purified as described in Example 31. The PBTPAPQ-F polymer obtained had the following characteristics: [η] = 0.65 dL/g

(25°C, 0.5 mol % DCP/m-cresol); FT-IR (KBr,cm-¹): 1616, 1585, 1543, 1518, 1487, 1447, 1433, 1358, 1290, 1270, 1227 (s), 1156, 1100, 1064, 1032, 877, 835, 799, 758, 619, 589; Anal, calcd. for (C₄₀H₂₀N₂S₂F₂)_n: C, 76.17; H, 3.2; N, 4.44. Found: C, 74.66; H, 3.87; N, 3.72.

EXAMPLE 34

Preparation of the copolymer PBTPQ/PBTPQA-OCH₃ (molar ratio of 80:20), respectively: 0.255 mmole of 4,4'-diamino-3,3'-di-p-methoxybenzoyldiphenyl-1,1'-acetylene (Compound 8), 1.02 mmol of 3,3'-dibenzoylbenzidine and 1.275 mmol of 5,5'-diacetyl-2,2'-bithiophene were mixed together in a reaction medium of 12 g DCP and 2 g m-cresol. After the reactor was purged with argon for 10 - 15 min., the temperature was raised slowly to 90°C. The reaction was run at this temperature for 9 h and then at 110°C for 15 h followed by 135 - 140°C for addition 24 h under static argon. As the viscosity of the reaction mixture increased with time, additional m-cresol was added to the reaction mixture to facilitate efficient stirring. Thereafter the reaction was quenched, precipitated and purified as described in Example 31.

EXAMPLE 35

Preparation of the copolymer PBTPQ/PBTPQA-F (molar ratio of 80:20), respectively: 0.255 mmole of 4,4'-diamino-3,3'-di-o-fluorodibenzoyldiphenyl-1,1'-acetylene (Compound 11), 1.02 mmol of 3,3'-dibenzoylbenzidine and 1.275 mmol of 5,5'-diacetyl-2,2'-bithiophene were mixed together in a reaction medium of 12 g DCP and 2 g m-cresol. The reactor was purged with argon for 10 - 15 min. before the temperature was raised slowly to 90°C. The reaction was run at this temperature for 2 h and then at 100°C for 3 h followed by 130°C for additional 25 h under static argon. As the viscosity of the reaction mixture increased with time, additional m-cresol was added to the reaction mixture to facilitate efficient stirring. Thereafter the reaction was quenched, precipitated, and purified as described in Example 31.

EXAMPLE 36

POLYMER SOLUBILIZATION

(a) Solubility of polymers of the present invention in commercially available phosphates/m-cresol systems:

Separate 15 - 20 wt % solutions of phenylphosphate, triphenylphosphate, and dialkyl (e.g. diethylthiophosphate, bis(2-ethylhexyl) hydrogen phosphate) phosphate were made in m-cresol at or near room temperature (about 40°C) by stirring 0.3 - 0.4 g of the respective phosphate in 2 g of solution made in freshly distilled m-cresol in a 10-mL vial capped with a Teflon-lined cap. When a clear and transparent solution was obtained, 4 -5 mg of each of the polymers made in accordance with Examples 4-19 and 31-35 was individually added to the separate solutions, and the vial was purged with argon and capped. The mixture in the vial was then heated at 120 - 140°C for 4 - 48 h (depending on the rate of dissolution of polymer in different phosphates/m-cresol system) while the vial was shaken occasionally to ensure proper mixing. The mixtures were monitored for the signs of solubilization such as swelling, color change, viscosity change, etc.

(b) Solubility of polymers in pure phosphates: An 8 - 20 mg sample of each of the polymers made in Examples 4- 19 and 31-35 were added to 2g of diphenyl phosphate and separately to dialkyl phospate in a 10-mL vial, and the vial was purged with argon before capping it with a Teflon-lined cap (in the case of solid phosphates, the mixture was gently warmed to allow the phosphates to melt before the purging was carried out). The mixture in the vial was then heated at 120 - 140°C for 4 - 48 h (depending on the different rate of dissolution in different phosphates) while the vial was shaken occasionally to ensure proper mixing and solubilization.

(c) Solubility of polymer-diphenyl phosphate (DPP) complexes in commercial available solvents: A 15 - 20 mg sample of 0.5 - 1.0 wt % solution of each of the polymers of Examples 4-19 and 31-35, in DPP, prepared as described above, was added in 1 mL of the solvent under test. This mixture was stirred at room temperature until a true solution was obtained or the polymer was precipitated.

(d) Solubility of polymers using a Lewis acid: Each of the polymers of Examples 4-19 and 31-35 was solubilized in accordance with the method of the present invention using a Lewis acid of AlCl₃ or GaCl₃. Due to the moisture sensitivity of metal halide Lewis acids, the solution preparations were performed inside a glovebox filled with dry nitrogen. A Vacuum Atmosphere Dri Lab glovebox was equipped with a Dri Train to remove residual water vapors or oxygen to below 5 ppm. Once prepared, the solutions were taken out of the glovebox if required for any processing. In solubilizing each of the foregoing polymers, 0.02 g of polymer was added, in a 10 mL vial, to 2 g of a 15 wt % solution of GaCl₃ or AlCl₃ prepared in nitromethane. The mixture was stirred using a magnetic stir bar at 40°C until a pure solution containing the polymer was obtained.

EXAMPLE 37

POLYMER PROCESSING TO THIN FILMS ON A SUBSTRATE

(a) Processing from diphenyl phosphate solutions: A solution of 0.1 - 0.5 wt % of each of the polymers of Examples 4-19 and 31-35 was prepared in DPP using the method described in Example 36(c). A fused silica substrate of 5-cm diameter was then cleaned with soap and water followed by acetone and finally with tetrahydrofuran before drying in an oven. The substrate as well as the solution was heated in an oven at 125°C.

This allowed the otherwise highly viscous or solid DPP-polymer solution to easily flow during the spinning process. The heated solution was poured onto the heated substrate and was immediately spun at 4350 rpm for 60s. The coated substrate was removed and placed in a 10% triethylamino (TEA)/ethanol mixture for regeneration to the pure polymer. The precipitation was completed by placing the coated film for 1 - 2 days in the nonsolvent mixture. The process is expedited by replacing nonsolvents every 12 h and by gently stirring the mixture while heating it at about 40°C. Uniform, transparent thin-film coatings were obtained and used for the study of optical properties.

(b) Processing from DPP/nitromethane (NM), DPP/nitromethane (NE), DPP/dichloromethane (DCE), and DPP/dichloromethane (PCM) solutions): A solution of 0.1 - 0.2 wt % of each of the polymers of Examples 4-19 and 31-35 was prepared by stirring 1 - 2 mg of the polymer in 2 g of solution made in 15 wt % DPP in nitromethane at 40°C. A fused silica substrate was cleaned and dried as described above in part (a). The solution was poured onto the substrate at room temperature and immediately spun at 1800 - 2500 rpm for 10 - 20 s. Nitromethane, being volatile, evaporated while the film was being spun, and a polymer-DPP complex was obtained as a result. The coated substrate was removed and precipitated in 10% TEA/ethanol mixture and worked up as described in part (a), above. The uniform, thin-film coatings thus obtained were dried in a vacuum at 60°C.

(c) Processing from GaCl₃/nitromethane (NM) or AlCl₃/nitromethane solutions: Polymers exemplified herein were processed to thin films on substrates by spin coating as follows: A solution containing 0.2 - 0.7 wt % polymer was prepared in GaCl₃/NM or AlCl₃/NM as described in Example 36(d). A fused silica substrate of 5-cm diameter was cleaned using soap and water followed by acetone and was dried. The solution was poured onto the substrate and immediately spun at 2000 rpm for 5 - 10 s. The avoid premature precipitation of the polymer due to the contact with moisture in air, the exposure time of the solution to the atmosphere before spinning was minimized. The coating thus obtained was regenerated slowly by keeping it in atmosphere for 4 - 5 h. The regeneration was completed by placing the coatings in methanol for 1 h followed by placement in water overnight. The uniform film so obtained was dried in a vacuum at 60°C.

EXAMPLE 38

POLYMER PROCESSING INTO FREESTANDING OBJECT

Polymers of the present invention were processed into freestanding films supported in frames as follows: A round hole (or any other desirable shape) of 1-in.

diameter was punched out in a sheet of material, such as Bakelite, copper, tin, steel and poster paper sheets, about 1-2 mm thick, and used as a frame. Using a sharp edge blade, fine, deep (about 1 mm) incisions were made all around the circumference of the hole (see Figure 1A). A sufficiently high density of incisions were necessary for the holes made in metal and Bakelite sheets in order to properly attach the regenerated polymer films to the frame. Once a frame was prepared, it was cleaned using acetone and a high pressure air jet. The frame was then placed on a clean flat glass plate of approximately the same dimensions and the two were tightly clamped together. The clamped assembly, with the circular cavity facing upward, was placed on a stand or a flat surface and was adjusted so as to level the glass plate in the horizontal plane. A 1 - 2 wt % solution of a polymer of the present invention, prepared as described in Example 36, was poured into the cavity (see Figure 1B). Using the edge of a knife or of a thin cover glass slide, the surface was smoothed out. Any air bubble pockets or other defects were removed by allowing the filled solution to stand. This assembly, with the polymer solution in the cavity, was carefully placed into the vacuum oven and the more volatile component of the solution system was allowed to be slowly evaporated (see Figure 1C). When a Lewis acid/nitroalkane solution, as described in Example 36(d), was used the cavity filling and the solvent evaporation were all carried out inside the glovebox to avoid premature regeneration of the polymer. The remaining highly viscous solution or film of the complex was precipitated by immersing the assembly in a glass container filed with a nonsolvent system (see Figure 1C). The precipitation was completed by carrying out the extraction for 1 - 2 days at either room temperature or 40 - 50°C, depending on the thickness of the film and the solvent system used. A 10% solution of triethylamine in ethanol was used for the precipitation of phosphate complexes, while methanol followed by water was employed in the case of Lewis acid complexes formed when the solubilizing method of the present invention was used. The clamps were removed from the assembly, and the film, along with the frame, was carefully separated from the glass plate. This was washed again in fresh nonsolvent and dried overnight in a vacuum oven at 60°C. A wrinkle-free, uniform, film of polymer held in the inside circumference of the hole was obtained as a result of the process (see Figure 1D). Thicker (thinner) films of the polymer were easily obtained by increasing (decreasing) the concentration of the polymer solution or by increasing (decreasing) the thickness of the frame or both.

EXAMPLE 39

POLYMERIC CHARACTERIZATION

Physical Properties: Intrinsic viscosity was measured using dilute solutions in the range of 0.05 - 0.02 g/dL in 0.1 mol % DCP/m-cresol at 25°C. The Fourier Transform Infrared (FT-IR) spectra of the free standing polymer films, formed as described in Example 36, were recorded on a Nicolet FT-IR spectrometer. In the case of polymers where free standing films, were not fabricated, such as in the case of polymers with low intrinsic viscosity, they were powdered and blended with KBr to make compressed pellets which were then used to obtain FT-IR spectra. ¹H NMR spectra were obtained on a GE 300 MHz NMR spectrometer. Thermal analysis of pressed polymer powder or films were performed on a Du Pont Thermal Analyst 2100 equipped with 951 thermogravimetric analyzer (TGA). Concentrated solutions of polymers (> 5 wt %) in DCP/m-cresol (1:3) were obtained by heating a polymer-solvent mixture in an oil-bath at 135°C for 4-6 h. The solutions were occasionally stirred during heating to obtain a homogeneous polymer concentration throughout the solution.

The thickness of the polymer films coated on silica substrates, as formed in Example 37, was measured using Alfa step 200 (Tencor Instruments) with an accuracy of + 0.005 μm, and the thickness of the much thicker freestanding films, supported on the frames, as formed in Example 37, was measured using an electronic micrometer with an accuracy of + 1 μm.

Optical Properties: Optical absorption spectra of polymer thin films, as shown in Figures 2, 3, 4, 5, 8, and 9, were obtained from thin coatings of the polymers on fused silica substrate formed in accordance with Example 37 on a Perkin-Elmer UV/vis/NIR spectrophotometer (Model Lambda 9). Similarly, solution spectra of polymer, as shown in Figures 6, 7, and 10, were obtained by using dilute solutions of polymers in 0.1 mol %

DCP/m-cresol solvent.

Optical losses were, estimated using two different methods: (1) Extrapolation from solution optical losses: the polymer solutions of various concentration (1-7 wt %) were prepared in 25 wt % DPP/m-cresol solvent system using the methodology described Example 36. The absorption spectra were recorded for all the polymer concentrations by placing the highly viscous solutions between two optically flat silica substrates while maintaining a constant optical path length of 125 urn using standard spacers. Optical losses for the pure polymer were then estimated by extrapolating the linear plot of absorbance versus polymer concentration to 100 wt % polymer. (2) Direct measurement in solid state: Freestanding polymer films of various thicknesses were prepared according to the technique described above. The absorption spectra were recorded for 3 - 4 films of different thicknesses, and the optical losses were calculated from the slope of the straight line obtained by plotting absorption losses versus the thickness of the films.

Refractive indexes of the films of polymers in the transparent region 500 - 3000 nm were obtained using the method described by Swanepoel, et al. J. Opt. Soc. Am. (1985), 2 , 1339, the contents of which are incorporated herein by reference. Various physical and optical properties of known polymers, PPQ, PPPQ, PBPQ, PSPQ, PPDA and PBDA, and polymers and copolymers of the present invention are presented in Table 1, below:

TABLE 1

Maximum Optical

Intrinsic Absorbance Bandgap Extinction

Viscosity, Decomposition λ_max Eg λ_max Coefficient

Polymer [η ] dL/g Temperature, ºC film (nm) film (eV) (Boln.)^a (nm) logs^a

PPQ 0.95 580 410 2.65 389 4.16

PPPQ 18.5 590 398 2.78 405 4.63

PBPQ 6.5 600 394 2.81 429 4.83

PSPQ ₃1.₃ 580 408 2.65 467 4.88

PPDA 3.05 590 443 2.47 442 4.49 ^PBDA 6.85 600 414 2.56 484 4.67

PBAPQ 8.9 600 399 2.72 436 4.86

PDMPQ 9.3 575 370 3.01 389 4.68

PBADA 7.65 590 426 2.57 490 4.65

PSDA 30.3 585 448 2.46 547 4.78

PDMDA 0.87 560 404 2.7 431 4.62

PTPQ 10.5 590 441 2.49 493 4.78 PBTPQ 11.5 590 468 2.33 546 5.06

PBTAPQ c 415 469 2.26 567 c

PBTVPQ 6.2 515 484 2.23 578 5.00

PTDA 1.2 565 498 2.17 572 4.49

PBTDA 2.3 600 520 2.07 659 4.90

PBTADA 4.4 415 525 2.0 709 4.72

PBTVDA 4.4 510 532 2.0 694 4.85

PBTPQA 0.89 470 448 2.36 543 4.81

PBTPQA-OCH₃ 1.10 465 444 7.36 537 4.70

PBTPQA-F 0.65 465 455 2.33 554 4.76

PBTPQ/ 3.6 525 459 2.36 543 5.07

PBTPQA-OCH₃

(80:20)

PBTPQ/ 1.9 530 462 2.33 545 4.94 PBTPQA-F

(80:20)

PBPQ/PBAPQ 25 - 397 2.79 431 4.88

PSPQ/PBAPQ 14.3 - 404 2.72 445 4.81

PSPQ/PBPQ 22.6 - 402 2.72 440 4.77

a Solutions made in 0.1 mol % DCP/m-cresol; ^b Determined by TGA at 10°c/min. under N₂; ^c Polymer not completely soluble. As seen in Table 1 above, the polymers of the present invention have high thermally stability, with thermal transitions (glass transition and melting point) occurring at temperature greater than 250°C. The decomposition temperature as determined by thermogravimetric analysis of the polymers under nitrogen at 10°C/min. was found to be generally greater than 550°C. Surprisingly, the diphenylmethane linked nonconjugated polymers of the present invention, PDMPQ and PDMDA, were also found to be stable above 550°C; slightly lower thermal stability was exhibited by polymers containing bithienylacetylene or bithienylvinylene linkages. The polymers with bithienylvinylene linkage (PBTVPQ and PBTVDA) showed an onset of decomposition at about 510°C, whereas the polymers with bithienylacetylene linkage (PBTAPQ and PBTADA) started decomposing at about 415°C. The slightly lower decomposition temperature of these polymers is attributable to the lower thermal stability of bithienylvinylene or bithienylacetylene linkages in them. Also ^as apparent in Table 1, polymers of the present invention having a repeating unit of structure (II), generally associated with the polyanthrazoline family of polymers, had a higher λ_max and a smaller Eg compared to their structure (I) counterparts.

The optical absorption spectra of thin films of the thiophene linked polymers of select polymers of the present invention are shown in Figures 2-5, 8, and 9 in comparison to known polymers; important optical properties of these polymers are shown at Table 1 above. As can be seen from the Figures 2-5, replacement of biphenylene linkage with bithiophene linkage resulted in a significant red shift of the absorption spectra ( λ_max ) of the polymers. The λ_max has increased by about 74 nm from PBPQ to PBTPQ. Similarly, a red shift of about 105 nm in λ_max can be observed in PBTDA compared to PBDA. In both cases, when the biphenylene linkage was replaced by a bithiophene linkage, the band gap was reduced by about 0.5 eV (Table 1). Compared to the phenylene linked polymers PPPQ and PPDA, the single thiophene linked polymers PTPQ and PTDA have higher λ_max by about 45 nm and smaller band gap by -0.3 eV, respectively. Another difference between the optical absorption spectra of the two types of polymer series was the ratio of oscillator strength of the lowest energy transition to that of the higher energy transitions. In thiophene linked polymers, this ratio was significantly higher compared to that seen in phenylene linked polymers.

These results suggest that by reducing steric hinderance, the thiophene linkage provided a more planar conjugated backbone in the polymers. Also, the possible delocalization of the lone pair electrons of the sulphur atom in a thiophene ring might contribute to provide a higher n-electron density in the thiophene linked conjugated polymers of the present invention.

Similar to the case of biphenylene linked polymers, the introduction of an acetylene or vinylene group between the two thiophene units of a bithiophene linked polymer was expected to facilitate further the π-electron delocalization. As can be seen from Figures 2-5, and Table 1, the value of λ_max is broadly in the order PBTPQ < PBTAPQ < PBTVPQ < PBTDA < PBTADA < PBTVDA and the band gap is in the order PBTPQ > PBTAPQ > PBTVPQ > PBTDA > PBTADA > PBTVDA. Also of note was the effect of the anthrazoline unit in polyanthrazolines versus bis(quinoline) unit in polyquinolines. Steric hindrance provided by the ortho- hydrogens adjacent to the single bond connecting two quinoline rings in bis(quinoline) unit forces the polymer segments to be noncoplanar, thereby, significantly reducing π-electron delocalization along the conjugated backbone. However, due to the three fused ring structure of anthrazoline, the steric hindrance in this region is eliminated in the polyanthrazolines. Therefore, compared to the polyquinolines (PQ series), polyanthrazolines (DA series) with the same linking group show higher λ_max and smaller band gap.

The results of the λ_max and band gap values of the thiophene linked polyanthrazolines (Table 1) also show that the optical properties of the block copolymers can be as good or better than those of the best homo-polymers, in this case polythiophene.

The solution optical absorption spectra of the polyquinolines and polyanthrazolines in 0.1 mole %

DCP/m-cresol are presented in Figures 6, 7, and 8.

Again, compared to the phenylene linked polymers (PBPQ, PBDA, PPPQ and PPDA), the thiophene linked polymers (PBTPQ, PBTDA, PTPQ and PTDA) exhibited a dramatic red shift of the λ_max. For the same set of polymers, these bathochromic shifts are stronger in solutions than in solid state films. Also, compared to the thin films of the polymers, their solutions in DCP/m-cresol show a much higher λ_max . The explanation lies in the fact that in solution, the nitrogen atom of the heterocyclic ring forms an acid-base complex with di-m-cresyl phosphate, i.e. by protonation, giving a more planar polymer back bone conformation. These solution optical spectra also confirm the systematic trends seen in the variation of thin film optical spectra with molecular structure.

The measured linear refractive index n_o, for polymers of the present invention are shown in Table 2, below, in comparison with these of known polymers.

TABLE 2

n_o

Polymer Measured

PPQ

PPPQ 1.69

PBPQ 1.79

PBAPQ 1.87

PSPQ 1.78

PPDA 1.68

PBDA 1.79

PBADA 1.75

PSDA 1.83

a At wavelengths greater than 1500 nm.

The linear refractive index, n_o, is an essential property of interest in optical materials in general and also a needed information for measuring or calculating the nonlinear optical properties of a material. Using the method related in J. Opt. Soc. Am. A., the refractive index of the indicated polymers in the transparent region of 500 - 3000 nm was measured. The accuracy in the measured values of n_o was + 5%. The refractive index spectra of representative members of the polyquinolines II and the polyanthrazolines III are shown in Figures 11 and 12, respectively. The refractive indexes are quite high for organic polymers. Far away from the absorption edge, the index of refraction values are between 1.68 and 1.87 in the wavelength range 900 - 3000 nm. However, due to dispersion, as the absorption edge at 500 nm is approached the n_o values increase to greater than 2. These results also suggest that the poly¬quinolines can be used as waveguides on glass, silica or related substrates which have lower index of refraction (-1.50 - 1.60).

The use of the polymers of the present invention as optical waveguides or as nonlinear optical materials for cubic nonlinear optics requires that optical loss α(cm^-1) from all sources, including intrinsic absorption and light scattering due to defects in morphology, be as small as possible. In the case of nonlinear optical materials, for example, a material figure of merit Re[X⁽³⁾]/α is usually to be maximized, wherein Re[X⁽³⁾] is the real part of the third-order optical nonlinearity and α is the optical loss at the frequency of intended application of the materials. We have determined the intrinsic optical loss in several polyquinolines using ^two different methods. In the first method, optical losses obtained for different concentrations of polymer solutions in DPP/m-cresol were extrapolated to 100 wt % polymer solution (i.e., pure polymer). The values obtained are shown in Table 3, below:

TABLE 3

Intrinsic Opticail Loss opt loss (α) at λ, cm^-1

Polymer 800 nm 1200 nm 1500 nm 1900 nm

PPQ 15.5 9.8 6.0 9.2

PBPQ 2.5 2.8 4.5 6.4 PBAPQ 9.0 8.8 10.7 13.2

PSPQ 3.7 1.1 1.0 2.2

PBAPQ^a 1.0 2.5 2.5 4.5 a Measured from thin films.

The values obtained varied from about 1 to 15.5 cm^-1 in the transparent region of 0.8 - 1.9 μm, shown in Table 3, and are orders of magnitude better than many other classes of conjugated polymer reported to date.

Claims

WHAT IS CLAIMED IS:

1. A polymer comprising a repeating unit of structure (I) or (II):

wherein X₁, X₄, X₅ and X₈ are each independently nitrogen or CR₂; X₂, X₃, X₆ and X₇ are each independently nitrogen or CR₂ when not forming point of attachment for said repeating unit to adjacent repeating units and are carbon when forming point of attachment, with the proviso that at least one but no more than two of X₁ , X₂, X₃ and X₄ is nitrogen and at least one but no more than two of X₅, X₆, X₇ and X₈ is nitrogen;

R₁ is lower alkenylene, lower alkynylene or a bivalent radical having structure (i):

wherein o is zero or 1, p is zero or 1, g is an integer from 1 to 10, Ar is a nitrogen, oxygen or sulfur-con taining heterocyclic moiety, a monocyclic or polycyclic aromatic moiety any of which moieties may be unsubstituted or substituted with one or more lower alkyl, lower alkoxy, cyano, or nitro groups, W₁ is lower alkylene, lower alkenylene or lower alkynylene;

each R₂ is independently hydrogen, nitro, cyano, halogen, or lower alkyl, lower alkoxy, lower alkaryl, aralkyl, aryl or a nitrogen, oxygen, or sulfur-containing heterocyclic moiety any of which may be unsubstituted or substituted with one or more halogen, lower alkyl, lower alkoxy or aroxy;

W is lower alkylene, lower alkenylene or lower alkynylene; and m is zero or 1, with the proviso that R₁ is other than phenylene, biphenylene, or stilbene when said repeating unit has structure (I) where m is zero and q is 1; and R₁ is other than phenylene or biphenylene when said repeating unit has structure (II) and g is 1.

2. The polymer of Claim 1 wherein X₁ is nitrogen and X₄ is CR₂.

3. The polymer of Claim 2 wherein X₂ is a first point of attachment to a first adjacent repeating unit and X₃ is CR₂.

4. The polymer of Claim 3 wherein X₅ is nitrogen and X₈ is CR₂.

5. The polymer of Claim 4 wherein X₆ is a second point of attachment to a second adjacent repeating unit and X ₇ is CR₂.

6. The polymer of Claim 5 wherein the R₂ associated with X₃ and the R₂ associated with X ₇ are each hydrogen.

7. The polymer of Claim 6 wherein the R₂ associated with X₄ is phenyl.

8. The polymer of Claim 7 wherein the R₂ associated with X₈ is phenyl.

9. The polymer of Claim 8 wherein said repeating unit has structure (I) and m is zero.

10. The polymer of Claim 9 wherein R₁ is alkenylene of 2 to 4 carbon atoms.

11. The polymer of Claim 10 wherein said repeating unit has the structure:

12. The polymer of Claim 9 wherein R₁ is an alkynylene of 2 to 4 carbon atoms.

13. The polymer of Claim 12 wherein said repeating unit has the structure:

14. The polymer of Claim 9 wherein R₁ has structure (i); o, p, and q are each 1; W₁ is alkylene of 3 to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety.

15. The polymer of Claim 14 wherein said repeating until has the structure:

16. The polymer of Claim 9 wherein R₁ has structure (i); o, p, and q are each 1; W_1. is alkynylene having 2 to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety.

17. The polymer of Claim 16 wherein said repeating unit has the structure:

18. The polymer of Claim 9 wherein R₁ has structure (i); o, and p are each zero; q is 1 and Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

19. The polymer of Claim 18 wherein said repeating unit has the structure:

20. The polymer of Claim 9 wherein R₁ has structure (i); o and p are each zero; and q is 2 and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

21. The polymer of Claim 20 wherein said repeating unit has the structure:

22. The polymer of Claim 9 wherein R₁ has structure (i); o, p, and g are each 1; W₁ is an alkenylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

23. The polymer of Claim 22 wherein said repeating unit has the structure:

24. The polymer of Claim 9 wherein R₁ has structure (i); o, p, and q are each 1; W₁ is an alkynylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

25. The polymer of Claim 24 wherein said repeating unit has the structure:

26. The polymer of Claim 3 wherein X₈ is nitrogen and X₅ is CR₂.

27. The polymer of Claim 26 wherein X₆ is CR₂ and X₇ is a second point of attachment to a second adjacent repeating unit.

28. The polymer of Claim 27 wherein the R₂ associated with X₃ and the R₂ associated with X₆ are each hydrogen.

29. The polymer of Claim 28 wherein the R₂ associated with X₄ is phenyl.

30. The polymer of Claim 29 wherein the R₂ associated with X₅ is phenyl.

31. The polymer of Claim 30 wherein said repeating unit has structure (II).

32. The polymer of Claim 31 wherein R₁ is alkenylene of 2 to 4 carbon atoms.

33. The polymer of Claim 32 wherein said repeating unit has the structure:

34. The polymer of Claim 31 wherein R₁ is alkynylene of 2 to 4 carbon atoms.

35. The polymer of Claim 34 wherein said repeating unit has the structure:

36. The polymer of Claim 31 wherein R₁ has structure (i); o, p, and q are each 1; W₁ is an alkylene of up to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety.

37. The polymer of Claim 36 wherein said repeating unit has the structure:

38. The polymer of Claim 31 wherein R₁ has structure (i); o, p, and q are each 1; W₁ is alkenylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety.

39. The polymer of Claim 38 wherein said repeating unit has the structure:

40. The polymer of Claim 31 wherein R₁ has structure (i); o, p, and q are each 1; W₁ is alkynylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety.

41. The polymer of Claim 40 wherein said repeating unit has the structure:

42. The polymer of Claim 31 wherein R₁ has structure (i); o and p are each zero; q is 1 and Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

43. The polymer of Claim 42 wherein said repeating unit has the structure:

44. The polymer of Claim 31 wherein R₁ has structure (i); o and p are each zero; q is 2 and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

45. The polymer of Claim 44 wherein said repeating unit has the structure:

46. The polymer of Claim 31 wherein R₁ has structure (i); o, p, and q are each 1; W₁ is alkenylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

47. The polymer of Claim 46 wherein said repeating unit has the structure:

48. The polymer of Claim 31 wherein R₁ has structure (i); o, p, and q are each 1; W₁ is alkynylene of 2 to 4 carbon atoms and each Ar is a bivalent radical for a sulfur-containing heterocyclic moiety.

49. The polymer of Claim 48 wherein said repeating unit has the structure:

50. The polymer of Claim 8 wherein said repeating unit has structure (I), m is 1 and W is alkynylene of 2 to 4 carbon atoms.

51. The polymer of Claim 50 wherein R₁ has structure (i); o and p are each zero; g is 2 and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

52. The polymer of Claim 51 wherein said repeating has the structure:

53. The polymer of Claim 50 wherein the phenyl associated with X₄ is a halogen-substituted phenyl and the phenyl associated with X₈ is a halogen-substituted phenyl.

54. The polymer of Claim 53 wherein said repeating unit has the structure:

55. The polymer of Claim 50 wherein the phenyl associated with X₄ is substituted with alkoxy of up to 4 carbon atoms and the phenyl associated with X₈ is substituted with alkoxy of up to 4 carbon atoms.

56. The polymer of Claim 55 wherein said repeating unit has the structure:

57. A copolymer comprising a first repeating unit of Claim 1 wherein said first repeating unit comprises a first structure (I) or (II) having a first R₁ and a second repeating unit of Claim 1 wherein said second repeating unit comprises second structure (I) or (II) having a second R₁ wherein said first R₁ is different from said second R₁.

58. A copolymer comprising at least one repeating unit of the type recited in Claim 1 with at least one repeating unit comprising PPQ, PBPQ, PPPQ, PSPQ, PBDA or PPDA.

59. The polymer of Claim 58 wherein said copolymer is a random copolymer.

60. The polymer of Claim 59 wherein said repeating unit has the structure:

61. The polymer of Claim 59 wherein said repeating unit has the structure:

62. The polymer of Claim 57 wherein said first structure (I) or (II) and said second structure (I) or (II) are present in substantially equal molar amounts.

63. A copolymer having a first repeating unit of the type recited in Claim 1 having a first R₁ and a second repeating unit of the type recited in Claim 1 having a second R₁ wherein said first R₁ and said second R₁ are the same and said first repeating unit and said second repeating unit are otherwise different.

64. The copolymer of Claim 63 wherein said copolymer is a random copolymer.

65. The polymer of Claim 64 wherein said repeating unit has the structure:

66. The polymer of Claim 64 wherein said repeating unit has the structure:

67. An article of manufacture comprising the polymer of Claim 1.

68. An article of manufacture comprising the polymer of Claim 11.

69. An article of manufacture comprising the polymer of Claim 13.

70. An article of manufacture comprising the polymer of Claim 15.

71. An article of manufacture comprising the polymer of Claim 17.

72. An article of manufacture comprising the polymer of Claim 19.

73. An article of manufacture comprising the polymer of Claim 21.

74. An article of manufacture comprising the polymer of Claim 23.

75. An article of manufacture comprising the polymer of Claim 25.

76. An article of manufacture comprising the polymer of Claim 33.

77. An article of manufacture comprising polymers of Claim 35.

78. An article of manufacture comprising the polymer of Claim 37.

79. An article of manufacture comprising the polymer of Claim 39.

80. An article of manufacture comprising the polymer of Claim 41.

81. An article of manufacture comprising the polymer of Claim 43.

82. An article of manufacture comprising the polymer of Claim 45.

83. An article of manufacture comprising the polymer of Claim 47.

84. An article of manufacture comprising the polymer of Claim 49.

85. An article of manufacture comprising the polymer of Claim 52.

86. An article of manufacture comprising the polymer of Claim 54.

87. An article of manufacture comprising the polymer of Claim 56.

88. An article of manufacture comprising the polymer of Claim 59.

89. An article of manufacture comprising the polymer of Claim 60.

90. An article of manufacture comprising the polymer of Claim 61.

91. An article of manufacture comprising the polymer of Claim 65.

92. An article of manufacture comprising the polymer of Claim 66.

93. The article of manufacture of Claim 67 wherein said polymer comprises a thin film, a fiber, a filament or a free-standing object.

94. The article of manufacture of Claim 67 comprising an electronic device.

95. The article of manufacture of Claim 67 comprising an optoelectrical device.

96. The article of manufacture of Claim 67 comprising a photonic device.

97. A method for solubilizing a polymer which comprises contacting a polymer of Claim 1, a polyquinoline, a polyanthrazoline or mixtures thereof with com plexing agent of a Lewis acid, a dialkyl phosphate or a diaryl phosphate under conditions effective to cause said polymer to become substantially soluble in a solvent.

98. The method of Claim 97 wherein said diaryl phosphate is diphenyl phosphate.

99. The method of Claim 97 wherein said Lewis acid is AlCl₃, GaCl₃, FeCl₃, SbF₅, SbCl₅, BF₃ or mixtures thereof.

100. The method of Claim 97 wherein said solvent is an aprotic organic solvent.

101. The method of Claim 100 wherein said solvent is nitromethane, nitroethane, 1-nitropropane, nitrobenzene, dichloromethane, dichloroethane, acetophenone, phenol or mixtures thereof.

102. The method of Claim 97 wherein said complexing agent is present in an amount of up to about 20% by weight based on said solvent.

103. The method of Claim 102 wherein said comp- lexing agent is present in an amount of up to about 15% by weight based on said solvent.

104. The method of Claim 103 wherein said complexing agent is present in an amount of up to about 10% by weight based on said solvent.

105. The method of Claim 104 wherein said complexing agent is present in an amount of up to about 5% by weight based on said solvent.

106. The method of Claim 97 wherein said polymer is present in an amount of up to about 3% by weight based on said complexing agent plus said solvent.

107. The method of Claim 106 wherein said polymer is present in an amount of up to about 2% by weight based on said complexing agent plus said solvent.

108. The method of Claim 107 wherein said polymer is present in an amount of up to about 1% by weight based on said complexing agent plus said solvent.

109. The method of Claim 108 wherein said polymer is present in an amount of up to about 0.5% by weight based on said complexing agent plus said solvent.

110. The method of Claim 109 wherein said polymer is present in an amount of up to about 0.1% by weight based on said complexing agent plus said solvent.

111. The method of Claim 98 wherein said polyquinoline or said polyanthrazoline has a rigid-rod conjugated structure.

112. The method of Claim 97 further comprising recovering said polymer.

113. The method of Claim 112 wherein said polymer is recovered by removing said solvent sufficient to obtain a remnant containing said polymer and contacting said remnant with a base under conditions effective to obtain said polymer from said remnant in substantially pure form.

114. The method of Claim 113 wherein said sol- vent is removed by evaporation.

115. The method of Claim 113 wherein said base is a Lewis base or a mixture of an alkylamine with a Lewis base.

116. The method of Claim 115 wherein said Lewis base is water, an alkanol of up to six carbon atoms, or mixtures thereof.

117. The method of Claim 115 wherein said alkylamine is triethylamine and said Lewis base is ethanol.

118. A method of forming an article of manufacture which comprises contacting a polymer of Claim 1, a polyquinoline, a polyanthrazoline or mixtures thereof with a complexing agent of a Lewis acid, a dialkyl phosphate or a diaryl phosphate under conditions effective to cause said polymer to become substantially soluble in a solvent to form a solution containing said polymer, processing said solution into a desired configuration and recovering said polymer from said solution under conditions effective to substantially maintain said polymer in said desired configuration.

119. The method of Claim 118 wherein said polyquinoline or polyanthrazoline has a rigid-rod conjugated structure.

120. The method of Claim 118 wherein said desired configuration is a thin film.

121. The method of Claim 118 wherein said processing comprises spin coating said solution onto the surface of a substrate under conditions effective to form a thin film of said solution on the surface of said substrate.

122. The method of Claim 121 wherein said recovering of said polymer comprises removing said solvent from said solution sufficient to obtain a thin film remnant containing said polymer on said surface of said substrate and contacting said thin film remnant with a base to obtain said polymer substantially as a thin film oⁿ said surface of said substrate.

123. The method of Claim 122 wherein said solvent is removed by evaporation.

124. The method of Claim 122 wherein said base is a Lewis base or a mixture of an alkylamine with a Lewis base.

125. The method of Claim 124 wherein said Lewis based is water, an alkanol of up to six carbon atoms, or mixtures thereof.

126. The method of Claim 125 wherein said alkylamine is triethylamine and said Lewis base is ethanol.

127. The method of Claim 118 wherein said desired configuration is a free-standing object.

128. The method of Claim 127 wherein said processing comprises placing said solution into a mold having said desired configuration.

129. The method of Claim 128 wherein said recovering of said polymer comprises removing said solvent from said solution in said mold sufficient to form a mold remnant containing said polymer and contacting said mold remnant with a Lewis base to obtain said polymer substantially in the shape of said mold.

130. The method of Claim 129 wherein said solvent is removed by evaporation.

131. The method of Claim 130 wherein said Lewis base is water or an alkanol of up to six carbon atoms or mixtures thereof.

132. The method of Claim 131 wherein said alkanol is methanol.

133. The method of Claim 129 further comprising removing said polymer from said mold.

134. The method of Claim 129 wherein said mold is a frame having an opening therethrough.

135. The method of Claim 134 wherein said desired configuration is a thin film spanning said opening.

136. The electronic device of Claim 94 wherein said polymer acts as a conductor.

137. The electronic device of Claim 136 wherein R₁ has structure (i) and Ar is a nitrogen, oxygen or sulfur-containing heterocyclic moiety any of which may be unsubstituted or substituted with lower alkyl, lower alkoxy, cyano or nitro groups.

138. The electronic device of Claim 136 wherein Ar is a sulfur-containing heterocyclic moiety and said polymer is p-doped.

139. The optoelectronic device of Claim 95 wherein said polymer forms a light emitting diode.

140. The optoelectronic device of Claim 137 wherein said light emitting diode is in the form of a flexible display device.

141. The photonic device of Claim 96 wherein said polymer acts as a waveguide.

142. The photonic device of Claim 96 wherein said polymer operates as an optical switch.

143. The polymer of Claim 18 wherein said sulfur-containing heterocyclic moiety is substituted with one or more lower alkoxy groups.

144. The polymer of Claim 143 wherein said repeating unit has the structure:

145. The polymer of Claim 20 wherein each sulfur-containing heterocyclic moiety is substituted with one or more lower alkoxy groups.

146. The polymer of Claim 145 wherein said repeating unit has the structure:

147. The polymer of Claim 9 wherein R₁ has structure (i); o and p are each zero; q is 3 and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

148. The polymer of Claim 147 wherein said repeating unit has the structure:

149. The polymer of Claim 42 wherein said sulfur-containing heterocyclic moiety is substituted with one or more lower alkoxy groups.

150. The polymer of Claim 149 wherein said repeating unit has the structure:

151. The polymer of Claim 44 wherein each sulfur-containing heterocyclic moiety is substituted with one or more lower alkoxy groups.

152. The polymer of Claim 151 wherein said repeating unit has the structure:

153. The polymer of Claim 31 wherein R₁ has structure (i); o and p are each zero; q is 3 and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

154. The polymer of Claim 153 wherein said repeating unit has the structure:

155. The polymer of Claim 8 wherein said repeat- ing unit has structure (I), m is 1 and W is alkenylene of 2 to 4 carbon atoms.

156. The polymer of Claim 155 wherein R₁ has structure (i); o, p, and q are each zero and Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

157. The polymer of Claim 156 wherein said repeating unit has the structure:

158. The polymer of Claim 155 wherein R₁ has structure (i); o and p are each zero; q is 2 and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

159. The polymer of Claim 158 wherein said repeating unit has the structure:

160. The polymer of Claim 155 wherein R₁ has structure (i); o, p, and q are each 1; W₁ is alkynylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

161. The polymer of Claim 160 wherein said repeating unit has the structure:

162. The polymer of Claim 155 wherein R₁ has structure (i); o, p, and q are each 1; W₁ is alkenylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.

163. The polymer of Claim 162 wherein said repeating unit has the structure:

164. The polymer of Claim 158 wherein each sulfur containing heterocyclic moiety is substituted with one or more lower alkoxy groups.

165. The polymer of Claim 164 wherein said repeating unit has the structure:

166. The polymer of Claim 155 wherein R₁ has structure (i); o and p are each zero; q is 3 and each Ar is a bivalent radical of a sulfur-containing heterocyclie moiety.

167. The polymer of Claim 166 wherein said repeating unit has the structure:

168. The polymer of Claim 159 wherein the phenyl associated with X₄ is substituted with one or more halogens and the phenyl associated with X₈ is substituted with one or more halogens.

169. The polymer of Claim 168 wherein said repeating unit has the structure:

170. The polymer of Claim 159 wherein the phenyl associated with X₄ is substituted with one ore more lower alkoxy groups and the phenyl associated with X₈ is substituted with one ore more lower alkoxy groups.

171. The polymer of Claim 170 wherein said repeating unit has the structure:

172. A copolymer comprising a repeating unit of the structure:

173. The optoelectronic device of Claim 95 wherein said device is an electrophotographic copying machine, a facsimile machine, or a laser printer.