CN103113415B - Thermostability Ni title complex with fluorescence property and preparation method thereof - Google Patents
Thermostability Ni title complex with fluorescence property and preparation method thereof Download PDFInfo
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- CN103113415B CN103113415B CN201210351486.4A CN201210351486A CN103113415B CN 103113415 B CN103113415 B CN 103113415B CN 201210351486 A CN201210351486 A CN 201210351486A CN 103113415 B CN103113415 B CN 103113415B
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Abstract
The present invention relates to thermostability Ni (II) title complex with fluorescence property and preparation method thereof, relate to transition-metal coordination technical field of polymer.Coordination chemistry formula is: [Ni (pgly) 2] n2nH2O, and wherein pgly is N-(2-picolyl) glycine anion part.The preparation technology of this title complex adopts nickel acetate and N-(2-picolyl) glycine as reaction raw materials, under low-temperature solvent heat condition, to be obtained by reacting crystalline material.Synthetic method mild condition of the present invention, productive rate are high, easy to operate, favorable reproducibility.Complex crystal sample has good fluorescent effect, and thermal analysis is fine, has good application prospect in fluorescent material.
Description
Technical field
The present invention relates to transition-metal coordination technical field of polymer, relate in particular to a kind of N-(2-picolyl)-nickel glycinate (II) title complex and preparation method thereof, described nickel complex crystal prototype emission wavelength be 425 and 433nm place have very strong fluorescent effect, and this title complex has higher thermostability, be expected to further be applied in crystalline state fluorescent material field.
Background technology
Novel metal-the organic framework material in a large number in recent years with stable micropore or meso-hole structure is successfully synthesized, this polyporous materials is showing potential wide application prospect (D.J.Tranchemontagne in the field such as optical, electrical, magnetic, catalysis, fractionation by adsorption, ion-exchange, gas storage, J.L.Mendoza-Cort é s, M.O ' Keeffe, O.M.Yaghi, Chem.Soc.Rev.2009,38,1257 – 1283.G.F é rey, C.Serre, Chem.Soc.Rev.2009,38,1380 – 1399.).Natural amino acid is the essentially consist unit of protein, its side chain has coordination mode and good hydrogen bond assembling ability flexibly, delicate impact can be produced to the structure and function of protein, the idealized unit cell (A.C.Kathalikkattil, K.K.Bisht, the N.A.Alcalde that construct functional complexes, E.Suresh, Cryst.Growth Des.2011,11,1631 – 1641.); But only use amino acid to be difficult to construct out the title complex supramolecular materials with specific physico-chemical property as part; by there is the functional group of stronger coordination ability as pyridine groups in aminoterminal introducing; itself and amino acid whose hydroxy-acid group are worked in coordination with assemble; stable porous organo-metallic skeleton material (L.A.Meiske can be constructed out; R.A.Jacobson, R.J.Angelici, Inorg.Chem.1980; 19,2028 – 2034; X.Li, T.liu, B.Hu, G.Li, H.Zhang, R.Gao, Cryst.Growth Des.2010,10,3051 – 3059).N-(2-picolyl)-glycine Zeng Zuowei physiologically active part constructs copper, cobalt and Zn complex (X.Wang, J.J.Vittal, Inorg.Chem.2003,42,5135 – 5138.X; Wang, J.D.Ranford, J.J.Vittal J.Mol.Struct.2006,796,28 – 35; T.Ama, K.Okamoto, T.Yonemura, H.Kawaguchi, A.Takeuchi, T.Yasui, Chem.Lett.1997,1189 – 1190), and relevant nickel complex there is not been reported, the nickel complex of ad hoc structure also can be used as fluorescent material (Z.Lu, L.Wen, Z.Ni simultaneously, Y.Li, H.Zhu, Q.Meng, Cryst.Growth Des.2007,7,268-274).
In view of this, inventor spy proposes a kind of N-(2-picolyl)-nickel glycinate (II) title complex and the preparation technology thereof with fluorescent characteristic, to fill up the blank of domestic and international association area.
Summary of the invention
The object of the invention is open a kind of N-(2-picolyl)-nickel glycinate (II) title complex, this title complex can be used as fluorescent material application, Heat stability is good and preparation method is simple, and productive rate is high, reproducibility is good, overcomes deficiency of the prior art.
The chemical formula that the present invention has thermostability nickel (II) title complex of fluorescence property is: [Ni (pgly)
2] 2H
2o, wherein pgly=N-(2-picolyl)-glycine anion part, its molecular formula is as follows:
The complex structure unit that the present invention relates to is: this title complex belongs to oblique system, and spacer is P2
1/ c, unit cell parameters is: a=8.9845 (7), b=9.4601 (8),
α=90 °, β=91.4140 (10) °, γ=90 °, its basic coordination structure is a monokaryon unit.
The title complex of described nickel (II) has two-dimentional hydrogen bond network structure, and wherein, each Ni (II) metal center is octahedra hexa-coordinate configuration, respectively with 2 pgly parts and two water molecule coordination.Each pgly part connects Ni (II) ion with tripodia chelated forms.
There is the preparation method of the title complex of the thermostability nickel (II) of fluorescence property, carry out according to following step:
At room temperature 20 DEG C, the nickel salt of metering and N-(2-picolyl)-glycine are dissolved in 1, in the mixed solvent of 4-dioxane and water, in hydrothermal reaction kettle, in 360min, temperature from ambient is raised to temperature of reaction gradually, be incubated 3 days at the reaction temperatures, then in 360min, temperature is cooled to room temperature 20 DEG C from temperature programming, obtain the purple granular crystals of title complex, by it collecting by filtration, then methyl alcohol, washed with diethylether is used respectively, drying, can obtain the title complex of the thermostability nickel (II) with fluorescence property.
Wherein said Isosorbide-5-Nitrae-dioxane and the volume ratio of water are 2:1 ~ 1:2.
The mol ratio of wherein said nickel salt and N-(2-picolyl)-glycine is 1:1 ~ 1:1.5.
Wherein said nickel salt is the nickel salts such as nickel acetate, nickelous chloride, single nickel salt, hydrochloric acid nickel, nickelous nitrate or nickelous perchlorate.
Wherein said range of reaction temperature is 90 DEG C ~ 170 DEG C.
The present invention adopts solvent thermal reaction method and becomes a kind of nickel (II) title complex containing N-(2-picolyl)-glycine, required conversion unit is simple, operation is simple, reproducibility is good, and the title complex prepared has Heat stability is good, productive rate advantages of higher, is expected to be used widely at fluorescent crystal Material Field.
Accompanying drawing explanation
Fig. 1 is the coordination environment figure containing Ni (II) in N-(2-picolyl)-nickel glycinate (II) title complex;
Fig. 2 is containing the two-dimentional hydrogen bond network structure iron of N-(2-picolyl)-nickel glycinate (II) title complex along crystallography a direction;
Fig. 3 is the Solid fluorescene spectrum figure containing N-(2-picolyl)-nickel glycinate (II) title complex;
Fig. 4 is the thermal gravimetric analysis curve figure containing N-(2-picolyl)-nickel glycinate (II) title complex.
Embodiment
The preparation of experimental example 1 title complex:
1mmol N-(2-picolyl) glycine (156mg), 1mmol nickel acetate (248mg) are mixed in 7mL1,4-dioxane and water (volume ratio is 2:1), the mol ratio of wherein said nickel salt and N-(2-picolyl)-glycine is 1:1.Mixture in hydrothermal reaction kettle in 360min temperature be raised to 90 DEG C by room temperature gradually, 90 DEG C are incubated 3 days, and then in 360min, temperature drops to 20 DEG C gradually from 90 DEG C, and last room temperature is filtered and obtained purple particulate state monocrystalline, then 10mL methyl alcohol and 10mL washed with diethylether is used respectively, seasoning.Productive rate be 75%(based on pgly, lower with).
The preparation of experimental example 2 title complex:
1.5mmol N-(2-picolyl) glycine (234mg), 1mmol nickel acetate (248mg) are mixed in 7mL1,4-dioxane and water (volume ratio is 2:1), the mol ratio of wherein said nickel salt and N-(2-picolyl)-glycine is 1:1.5.Mixture in hydrothermal reaction kettle in 360min temperature from ambient be raised to 90 DEG C gradually, 90 DEG C are incubated 3 days, and then in 360min, temperature drops to 20 DEG C gradually from 90 DEG C, and last room temperature is filtered and obtained purple particulate state monocrystalline, then 10mL methyl alcohol and 10mL washed with diethylether is used respectively, seasoning.Productive rate is 69%.
The preparation of experimental example 3 title complex:
1mmol N-(2-picolyl) glycine (156mg), 1mmol nickel acetate (248mg) are mixed in 7mL1,4-dioxane and water (volume ratio is 1:2), the mol ratio of wherein said nickel salt and N-(2-picolyl)-glycine is 1:1.Mixture in hydrothermal reaction kettle in 360min temperature from ambient be raised to 90 DEG C gradually, 90 DEG C are incubated 3 days, and then in 360min, temperature drops to 20 DEG C gradually from 90 DEG C, and last room temperature is filtered and obtained purple particulate state monocrystalline, then 10mL methyl alcohol and 10mL washed with diethylether is used respectively, seasoning.Productive rate is 71%.
The preparation of experimental example 4 title complex:
1mmol N-(2-picolyl) glycine (156mg), 1mmol nickel acetate (248mg) are mixed in 7mL1,4-dioxane and water (volume ratio is 2:1), the mol ratio of wherein said nickel salt and N-(2-picolyl)-glycine is 1:1.Mixture in hydrothermal reaction kettle in 360min temperature from ambient be raised to 170 DEG C gradually, 170 DEG C are incubated 3 days, and then in 360min, temperature drops to 20 DEG C gradually from 170 DEG C, and last room temperature is filtered and obtained purple particulate state monocrystalline, then 10mL methyl alcohol and 10mL washed with diethylether is used respectively, seasoning.Productive rate is 67%.
The preparation of experimental example 5 title complex:
1.5mmol N-(2-picolyl) glycine (234mg), 1mmol nickel acetate (248mg) are mixed in 7mL1,4-dioxane and water (volume ratio is 2:1), the mol ratio of wherein said nickel salt and N-(2-picolyl)-glycine is 1:1.5.Mixture in hydrothermal reaction kettle in 360min temperature from ambient be raised to 100 DEG C gradually, keep 100 DEG C 3 days, then in 360min, temperature drops to 20 DEG C gradually from 100 DEG C, and last room temperature is filtered and obtained purple particulate state monocrystalline, then 10mL methyl alcohol and 10mL washed with diethylether is used respectively, seasoning.Productive rate is 67%.
The preparation of experimental example 6 title complex:
1mmol N-(2-picolyl) glycine (156mg), 1mmol nickelous nitrate (291mg) and 7mL1, the mixture of 4-dioxane and water (volume ratio is 1:2), the mol ratio of wherein said nickel salt and N-(2-picolyl)-glycine is 1:1.Mixture in hydrothermal reaction kettle in 360min temperature from ambient be raised to 170 DEG C gradually, 170 DEG C are incubated 3 days, and then in 360min, temperature drops to 20 DEG C gradually from 170 DEG C, and last room temperature is filtered and obtained purple particulate state monocrystalline, then 10mL methyl alcohol and 10mL washed with diethylether is used respectively, seasoning.Productive rate is 62%.
The sign of experimental example 7 title complex:
(1) structure determination of title complex
Crystal structure determination adopts Bruker Apex II CCD diffractometer, under 296 (2) K, with through graphite monochromatised Mo K alpha-ray
collect point diffraction with ω scan mode, the data of collection also carry out semiempirical absorption correction by SADABS method by SAINT programe reduction.Structure elucidation and refine adopt SHELXS and SHELXL of SHELXTL program to complete respectively, by complete matrix least square method to F
2carry out revising the coordinate and anisotropic parameters that obtain whole non-hydrogen atom.All hydrogen atoms are fixed on parent atom by theory in structure refinement process, give the isotropy displacement parameter of slightly larger than parent atom displacement parameter (C-H, 1.2 or O/N – H, 1.5 times).Detailed axonometry data are in table 1.Structure is shown in Fig. 1 and 2.Fig. 1: the coordination environment figure of nickel complex; Fig. 2: title complex two dimension hydrogen bond structure schematic diagram.
(2) the solid fluorescence performance study of title complex
Complex crystal sample after enrichment process, through further milled processed, carry out the test of solid fluorescence: title complex excites at 360nm place, obtain maximum emission peak at 425nm and 433nm place, see Fig. 3 (INSTRUMENT MODEL: Varian CaryEclipsespectrometer).
(3) thermostability of title complex characterizes
The thermogravimetric analysis of title complex shows it and appoints so energy stable existence at about 310 DEG C, has higher thermostability, ensures, see Fig. 4 (INSTRUMENT MODEL: TG/DTA-6300) for its further Application and Development as crystalline material provides thermostability.
Above example is only for illustration of content of the present invention, and in addition, the present invention also has other embodiment.But all employings are equal to replacement or the technical scheme that formed of equivalent deformation mode all drops in protection scope of the present invention.
The predominant crystal data of table 1 title complex
aR=∑||f
o|-|F
c||/∑|f
o|.
bR
w=[∑[w(F
o 2-F
c 2)
2]/∑w(F
o 2)
2]
1/2.
cGOF={∑[w(F
o 2-F
o 2)
2]/(n-p)}
1/2.
Claims (5)
1. there is thermostability nickel (II) title complex of fluorescence property, it is characterized in that its chemical formula is: [Ni (pgly)
2] 2H
2o, wherein pgly=N-(2-picolyl)-glycine anion part, its molecular formula is as follows:
；
Described nickel (II) title complex belongs to oblique system, and its basic coordination mechanism is a monokaryon unit; Described nickel (II) title complex has two-dimentional hydrogen bond network structure, and wherein, each Ni (II) metal center is octahedra hexa-coordinate configuration, respectively with 2 pgly parts and two water molecule coordination; Each pgly part connects Ni (II) ion with tripodia chelated forms;
The described title complex with the thermostability nickel (II) of fluorescence property is prepared according to following step: under room temperature, the nickel salt of metering and N-(2-picolyl)-glycine are dissolved in 1, in the mixed solvent of 4-dioxane and water, in hydrothermal reaction kettle, in 360 min, temperature from ambient is raised to temperature of reaction gradually, be incubated 3 days at the reaction temperatures, then in 360min, temperature is cooled to room temperature 20 DEG C from temperature programming, obtain the purple granular crystals of title complex, by it collecting by filtration, then methyl alcohol is used respectively, washed with diethylether, dry, the title complex of the thermostability nickel (II) with fluorescence property can be obtained,
Unit cell parameters is:
a=8.9845 (7),
b=9.4601 (8),
c=10.8054 (8), α=90 °, β=91.4140 (10) °, γ=90 °.
2. the title complex with the thermostability nickel (II) of fluorescence property according to claim 1, is characterized in that the volume ratio of wherein said Isosorbide-5-Nitrae-dioxane and water is 2:1 ~ 1:2.
3. the title complex with the thermostability nickel (II) of fluorescence property according to claim 1, is characterized in that the mol ratio of wherein said nickel salt and N-(2-picolyl)-glycine is 1:1 ~ 1:1.5.
4. the title complex with the thermostability nickel (II) of fluorescence property according to claim 1, is characterized in that wherein said nickel salt is nickel acetate, nickelous chloride, single nickel salt, hydrochloric acid nickel, nickelous nitrate or nickelous perchlorate.
5. the title complex with the thermostability nickel (II) of fluorescence property according to claim 1, is characterized in that wherein said range of reaction temperature is 90 DEG C ~ 170 DEG C.
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| CN106916174B (en) * | 2017-03-01 | 2018-10-09 | 河北师范大学 | A kind of chiral amino acid derivative complex, preparation method and applications |
| CN107325117A (en) * | 2017-07-07 | 2017-11-07 | 常州大学 | Structure of chiral silver complex of N pyridines threonine derivatives and preparation method thereof |
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Non-Patent Citations (3)
| Title |
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| Induction of photoluminescence and columnar mesomorphism in hemi-disc salphen type Schiff bases via nickel(II) coordination;Chira R. Bhattacharjee et al.;《Polyhedron》;20111213;第33卷(第1期);第417页摘要 * |
| Nature of the Reactants and Influence of Water on the Supramolecular Assembly;Xiaobai Wang et al.;《Inorganic Chemistry》;20030729;第42卷(第17期);第5135页摘要第3行，第5136页图1，第5141页右栏第3段 * |
| Photoluminescent Hemidisc-Shaped Liquid Crystalline Nickel(II) Schiff-Base Complexes;Chira R. Bhattacharjee et al.;《Europen Journal of Inorganic Chemistry》;20111111;第2011卷(第35期);第5390-5396页 * |
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