Search Results (298)

Figure 1
<p>(<b>a</b>) Single-capped tetragonal prism of Tb(III) in <b>1</b>, blue line, configuration bar; red bullet, oxygen atoms; green circle, Tb. The coordination environment of Zn(II) ions in <b>1</b>. (<b>b</b>) Hexanuclear Tb₆O₃₀ unit of <b>1</b>. (<b>c</b>) View of the 3D framework packing perpendicular to the <span class="html-italic">a</span>-axis. (<b>d</b>) The <b>fcu</b> topology network of <b>1</b>.</p> Full article ">Figure 2
<p>PXRD patterns of <b>1</b>.</p> Full article ">Figure 3
<p>(<b>a</b>) The fluorescence excitation and emission of <b>1</b> and H₂fdpdc ligand in solid state. (<b>b</b>) The cation-dependent fluorescence emission of <b>1</b>. (<b>c</b>) The luminescence intensity at 545 nm with the presence of different cations. (<b>d</b>) The luminescent emission spectra of <b>1</b> in Ba²⁺ solutions with different concentrations.</p> Full article ">Figure 4
<p>(<b>a</b>) The correlation between relative intensity and the addition of Ba²⁺ ion at different concentrations over time at 545 nm. (<b>b</b>) Calculated LOD of <b>1</b> in Ba²⁺ solutions.</p> Full article ">Figure 5
<p>(<b>a</b>) Luminescence intensity of <b>1</b> at 545 nm dispersed in water with the addition of different metal ions. The concentration of interferential metal ions and Ba²⁺ ion are both 1 mM. (<b>b</b>) Luminescence intensity (545 nm) of <b>1</b> during five recycling.</p> Full article ">Figure 6
<p>(<b>a</b>) N₂ sorption isotherm of <b>1a</b> at 77 K (the inset shows the pore size distribution). (<b>b</b>) Room temperature adsorption isotherms of C₂H₂, CO₂, N₂, H₂, CO, and CH₄ based on the simulation. (<b>c</b>) Isosteric heat of adsorption of C₂H₂ for <b>1</b> calculated based on molecular simulation isotherms at 298 K. (<b>d</b>) Selectivities for C₂H₂ in the equimolar C₂H₂/CO₂, C₂H₂/N₂, C₂H₂/H₂, C₂H₂/CO, and C₂H₂/CH₄ at 298 K from the simulation.</p> Full article ">

Graphical abstract
Full article ">Figure 1
<p>ORTEP view of the crystal structures of (<b>a</b>) <b>1</b> and (<b>b</b>) <b>3</b>. Crystallization water molecules and hydrogen atoms have been omitted for clarity, and ellipsoids represent 50% probability levels.</p> Full article ">Figure 2
<p>(<b>a</b>) Top and side views of the coordination polyhedron around the Nd1 metal center of <b>1</b> with the atom numbering scheme for the donor atoms, showing the distorted muffin geometry. The O1D/O3C/O3D atoms compose the triangular base, and the O1A/O1C/O3A/O3B/O1w atoms compose the pentagonal plane with the O1B atom in the capped position. (<b>b</b>) Top and side views of the coordination polyhedron around the Tb1 metal center of <b>3</b> with the atom numbering scheme for the donor atoms, showing the distorted capped square antiprism geometry. The O3A/O3B/O3C/O3D atoms compose the square base of the prism, and the O1A/O1B/O1C/O1D atoms compose the quadratic plane of the capped face with the O1W atom in the capped position.</p> Full article ">Figure 3
<p>(<b>a</b>) View of the supramolecular layers of hydrogen-bonded mononuclear units of <b>1</b> along the crystallographic <span class="html-italic">ab</span> plane. (<b>b</b>) View of the supramolecular layers of hydrogen-bonded mononuclear units of <b>3</b> along the crystallographic <span class="html-italic">ac</span> plane, showing the presence of additional hydrogen-bonded DMSO molecules. Cyan dashed lines represent hydrogen bonds. CH hydrogen atoms, remaining solvent molecules and tetrabutylammonium cations were omitted for the sake of clarity.</p> Full article ">Figure 4
<p>Views perpendicular to the layers growing onto the (<b>a</b>) <span class="html-italic">ab</span> plane in <b>1</b> and (<b>b</b>) <span class="html-italic">ac</span> plane in <b>3</b>. Three layers are depicted in each panel, while hydrogen atoms and solvent molecules were omitted for the sake of clarity. Color codes: carbon, gray; nitrogen, light blue; oxygen, red; Nd, light green; and terbium, green.</p> Full article ">Figure 5
<p><span class="html-italic">χ</span>_M<span class="html-italic">T</span> vs. <span class="html-italic">T</span> curves for <b>1</b>–<b>4</b> (<b>a</b>–<b>d</b>). Inset: <span class="html-italic">M</span> vs. <span class="html-italic">H</span> curves. Solid lines represent the best-fit curves according to the text.</p> Full article ">Figure 6
<p>(<b>a</b>) Representation of the easy magnetization axis of dysprosium(III) complex <b>4</b> as a red arrow in each single-ion magnet (color code: Dy in violet, N in blue, oxygen in red, carbon in grey). (<b>b</b>) The easy magnetization axis is represented by red arrows in the crystal packing of <b>4</b> along the crystallographic <span class="html-italic">ac</span> direction. For clarity, the hydrogen atoms, solvent molecules and counterions were omitted.</p> Full article ">Figure 7
<p>(<b>a</b>) <span class="html-italic">χ</span>_M′ and <span class="html-italic">χ</span>_M″ vs. <span class="html-italic">ν</span> curves of <b>1</b> under 1.0 kOe dc magnetic field. (<b>b</b>) Arrhenius plot of <b>1</b> under 1.0 kOe dc magnetic field. Solid lines represent fits to the data (see text).</p> Full article ">Figure 8
<p>(<b>a</b>) <span class="html-italic">χ</span>_M′ and <span class="html-italic">χ</span>_M″ vs<span class="html-italic">. ν</span> curves of <b>2</b> under 1.0 kOe dc magnetic field. (<b>b</b>) Arrhenius plot of <b>2</b> under a 1.0 kOe dc magnetic field. Solid lines represent fits to the data (see text).</p> Full article ">Figure 9
<p>(<b>a</b>) <span class="html-italic">χ</span>_M′ and <span class="html-italic">χ</span>_M″ vs. <span class="html-italic">ν</span> curves of <b>3</b> under 5.0 kOe dc magnetic field. (<b>b</b>) Arrhenius plot of <b>3</b> under 5.0 kOe dc magnetic field. Solid lines represent fits to the data (see text).</p> Full article ">Figure 10
<p><span class="html-italic">χ</span>_M′ and <span class="html-italic">χ</span>_M″ vs. <span class="html-italic">ν</span> curves of compound <b>4</b> under (<b>a</b>) zero dc magnetic field and (<b>b</b>) 1.0 kOe dc magnetic field. Arrhenius plots of <b>4</b> (<b>c</b>) under zero dc field and (<b>d</b>) 1.0 kOe dc field. Solid lines represent fits to the data (see text).</p> Full article ">Scheme 1
<p>(<b>a</b>) Chemical structure of the proligand <span class="html-italic">N</span>-(2,4,6-trimethylphenyl)oxamic acid ethyl ester (EtHtmpa) and (<b>b</b>) their mononuclear lanthanide(III) oxamate complexes.</p> Full article ">Scheme 2
<p>Synthetic procedure for complexes <b>1</b>–<b>4</b>.</p> Full article ">

Graphical abstract
Full article ">Figure 1
<p>Structural representations of the dinuclear complexes <b>1Yb</b> (<b>a</b>) and <b>1Er</b> (<b>b</b>) with thermal ellipsoids drawn at a 50% probability level. Hydrogen atoms and co-crystallized DCM molecules have been omitted for clarity. Color code: C (grey), N (blue), O (red), S (yellow), B (pink), Yb (green) and Er (light green).</p> Full article ">Figure 2
<p>Diffuse reflectance and emission spectra of Ln^III dinuclear complexes in the solid state. (<b>a</b>) UV-Vis range, showing ligand-centered absorption and emission (excitation at 350 nm). (<b>b</b>) NIR range, highlighting Ln^III-centered emission (excited at 355 nm) and vibrational absorption bands. Spectroscopic terms for the Ln^III upper manifolds, as well as key vibrational overtones and combination modes, are labeled. Diffuse reflectance spectra are represented by solid lines, while PL spectra are shown as dotted lines in both panels.</p> Full article ">Figure 3
<p>Time-resolved NIR PL of Ln^III dinuclear complexes in the solid state (excitation at 355 nm). Inset: Time-resolved and spectrally integrated Vis PL of Ln^III complexes in the solid state (excitation at 350 nm). Dots: Experimental data; Black lines: Biexponential decay fits; refer to the text for details.</p> Full article ">Scheme 1
<p>Synthesis of complexes <b>1Yb</b> and <b>1Er</b>.</p> Full article ">

Figure 1
<p>(<b>a</b>) The perspective view of the asymmetric unit of compound <b>1</b> with partial atoms labeled. Hydrogen atoms have been omitted for clarity. (<b>b</b>) The coordination geometry of the Dy1 ion (<b>left</b>) and Dy2 (<b>right</b>) ion in compound <b>1</b>. Color code: Dy^III, bright green; O, red; N, blue; P, plum; C, gray.</p> Full article ">Figure 2
<p>The connection mode of the semi-protonated hexacarboxylic acid ligand (<b>a</b>) and dinuclear unit (<b>b</b>) of compound <b>1</b>. Asymmetry code: A, x, 1/2 − y, −1/2 + z; B, 1 − x, −1/2 + y, 3/2 − z. Color code: Dy^III, bright green; O, red; N, blue; P, plum; C, gray; H, sky blue.</p> Full article ">Figure 3
<p>The 2D network structure of compound <b>1</b> with ten-membered metal rings along the a-axis.</p> Full article ">Figure 4
<p>(<b>a</b>) Plots of <span class="html-italic">χ</span>_M<span class="html-italic">T</span> vs. <span class="html-italic">T</span> for compound <b>1</b>. (<b>b</b>) <span class="html-italic">M</span> vs. <span class="html-italic">H</span> and <span class="html-italic">M</span> vs. <span class="html-italic">H</span>/<span class="html-italic">T</span> (inset) plots for compound <b>1</b> at 2–5 K. The solid lines show a guide for the eyes.</p> Full article ">Figure 5
<p>Temperature dependence of the in-phase and out-of-phase ac magnetic susceptibility signals at the indicated frequencies for compound <b>1</b> under the optimal dc field.</p> Full article ">Figure 6
<p>Room temperature solid-state emission spectra of compound <b>2</b> and H₆L under excitation of 352 nm.</p> Full article ">Scheme 1
<p>The structure of hexacarboxylic acid ligand H₆L used in this work.</p> Full article ">

Graphical abstract
Full article ">Figure 1
<p>The effect of DMDCHDGA concentration in the organic phase on the distribution ratio of Tf₂N⁻ anion between 0.01 M C₄mimTf₂N solutions in DCE and water.</p> Full article ">Figure 2
<p>IR spectra of DMDCHDGA (1), IL (2), and 0.1 M DMDCHDGA/IL solution (3). The most intense peak of the ligand (curve 1) is marked with the * symbol on the IR spectrum of the solution.</p> Full article ">Figure 3
<p>(<b>a,b</b>) Fragments of IR spectra of IL (curve 2) and 0.1 M DMDCHDGA/IL solution (curve 3).</p> Full article ">Figure 4
<p>IR spectra of solutions 0.1 M L/IL (1), 0.5 M DMDCHDGA/IL (2), and equimolar mixture of DMDCHDGA and IL (3).</p> Full article ">Figure 5
<p>Extraction of HTf₂N with 0.01 M DMDCHDGA solutions in DCE as a function of equilibrium HTf₂N concentration in the aqueous phase.</p> Full article ">Figure 6
<p>IR spectrum of the complex DMDCHDGA-HTf₂N.</p> Full article ">Figure 7
<p>The effect of DMDCHDGA concentration in the organic phase on the distribution ratio of Tf₂N⁻ anion between 0.01 M C₄mimTf₂N solutions in DCE and 0.1 M HNO₃ solutions.</p> Full article ">Figure 8
<p>The effect of HNO₃ and HCl concentration in the aqueous phase on the distribution ratio of Tf₂N⁻ anion between 0.02 M C₄mimTf₂N solutions in DCE and 0.02 M C₄mimTf₂N solutions in DCE containing 0.02 M DMDCHDGA.</p> Full article ">Figure 9
<p>The effect of HNO₃ concentration⁻ in the aqueous phase on the transfer of Tf₂N⁻ ions into the aqueous phase from IL phase in the presence of DMDCHDGA.</p> Full article ">Figure 10
<p>IR spectra of samples 3 (0.1 M DMDCHDGA/IL) and 4 (0.1 M DMDCHDGA/IL//3 M HNO₃).</p> Full article ">Figure 11
<p>The extraction of lanthanides(III) from 3 M HNO₃ solutions with 0.01 M DMDCHDGA and TODGA solutions in [C₄mim][Tf₂N] and DCE.</p> Full article ">Figure 12
<p>The effect of HNO₃ concentrations in the aqueous phase on the extraction of Ln(III) with 0.01 M solutions of DMDCHDGA in [C₄mim][Tf₂N].</p> Full article ">Figure 13
<p>The effect of NO₃⁻ (HNO₃ + NH₄NO₃) concentrations in the aqueous phase on the extraction of Ln(III) with 0.01 M solutions of DMDCHDGA in [C₄mim][Tf₂N]. [H⁺] = 2 M.</p> Full article ">Figure 14
<p>The effect of H⁺ concentrations in the aqueous phase on the extraction of Ln(III) with 0.01 M solutions of DMDCHDGA in [C₄mim][Tf₂N]. [NO₃⁻] = 5 M.</p> Full article ">Figure 15
<p>The effect of DMDCHDGA concentration in [C₄mim][Tf₂N] on the extraction of lanthanides(III) from 3 M HNO₃ solutions.</p> Full article ">Figure 16
<p>IR spectra of samples 4 (0.1 DMDCHDGA/IL//3 M HNO3) and 5 (0.1 DMDCHDGA/IL//3 M HNO₃ + Eu³⁺).</p> Full article ">Figure 17
<p>Difference IR spectra of samples 5 and 4 (curve 1) and 7 and 6 (curve 2).</p> Full article ">Figure 18
<p>The extraction of lanthanides(III) from 3 M HNO₃ solutions with 0.01 M DMDCHDGA solutions in undiluted ILs.</p> Full article ">Figure 19
<p>The effect of HNO₃ concentrations in the aqueous phase on the extraction of Eu(III) with 0.01 M solutions of DMDCHDGA in DCE and DCE containing 0.01 M C₄mimTf₂N.</p> Full article ">Figure 20
<p>The extraction of lanthanides(III) from 3 M HNO₃ and 3 M HCl solutions with 0.01 M DMDCHDGA solutions in DCE and DCE containing 0.01 M C₄mimTf₂N. At the Ln(III) extraction from 3 M HCl solutions in the absence of C₄mimTf₂N in the organic phase, the <span class="html-italic">D</span>_Ln values are &lt;10⁻².</p> Full article ">Figure 21
<p>The extraction of lanthanides(III) from 3 M HNO₃ solutions with 0.01 M DMDCHDGA and TODGA solutions in DCE containing 0.01 M ionic liquids.</p> Full article ">Scheme 1
<p>The structures of the studied DGAs and ILs.</p> Full article ">Scheme 2
<p>The scheme of N,N′-dimethyl-N,N′-dicyclohexyl-3-oxadiglycolamide (DMDCHDGA) synthesis.</p> Full article ">Scheme 3
<p>The scheme of benzyltriethylammonium bis(trifluoromethylsulfonyl)imide synthesis.</p> Full article ">

Graphical abstract
Full article ">Figure 1
<p>Structures of sucrose disaccharide (<b>1</b>) and newly designed synthetic ligand (<b>2</b>) using sucrose as a scaffold.</p> Full article ">Figure 2
<p>Recorded NMR spectra and signal assignments of compound <b>2</b> in D₂O. Top: 1D ¹H spectrum (400 MHz); bottom: 1D ¹³C spectrum with the expansion of the ~48.0–79.5 ppm region.</p> Full article ">Figure 3
<p>Recorded 2D ¹H-¹³C heteronuclear correlation NMR spectrum (400 MHz) of compound <b>2</b> in D₂O.</p> Full article ">Figure 4
<p>Potentiometric titrations of compound <b>2</b> (<b>left</b>). L: 0.5–3 µmol; extra HCl: 0–34.5 µmol in 0.1 M NMe₄Cl; total initial volume: 4.0 mL. Burette: [NMe₄OH] = 0.05 M, and calculated distribution curves (<b>right</b>) of different protonated species of compound <b>2</b> at different pHs: [compound <b>2</b>] = 5.0 × 10⁻⁴ M.</p> Full article ">Figure 5
<p>Electrospray ionization (negative) high-resolution spectrum (<b>top</b>) of formed 1:1 complex [GdL]⁻ with a molecular formula of C₂₆H₃₄N₈O₁₇Gd [M-H]⁻ between ligand <b>2</b> and Gd(III), and comparison to the isotope patterns of simulated mass spectrum (<b>bottom</b>).</p> Full article ">Figure 6
<p>ATR-FTIR spectra of ligand <b>2</b> (<b>left</b>) and ligand <b>2</b>/Gd(III) complex (<b>right</b>).</p> Full article ">Figure 7
<p>Potentiometric titrations of ligand <b>2</b> in the presence of gadolinium(III) (<b>left</b>). Seventeen titrations were performed. Ligand <b>2</b>: 2.0 µmol; extra HCl: 13.82 µmol in NMe₄Cl (0.1 M); total initial volume: 4.0 mL. Burette: [NMe₄OH] = 0.05 M. The calculated distribution curved of 1:1 complex during titration [Gd]t = [Ligand <b>2</b>] = 5.0 × 10⁻⁴ M (<b>right</b>).</p> Full article ">Figure 8
<p>p<span class="html-italic">Gd</span> value of Gd(III)-ligand <b>2</b> complexes as a function of pH. p<span class="html-italic">Gd</span> = −log[Gd]_free, [Gd]_total = 1.0 µM, and [ligand]_total = 10 µM.</p> Full article ">Figure 9
<p>The plot of 1/T₁ versus the concentration of ligand <b>2</b>/Gd(III) complex gives a linear line with a slope of 7.6958 mM⁻¹s⁻¹.</p> Full article ">Scheme 1
<p>Synthetic route to the designed target ligand (<b>2</b>) from sucrose (<b>1</b>).</p> Full article ">Scheme 2
<p>The major protonation states of target ligand <b>2</b> and their designated notations.</p> Full article ">Scheme 3
<p>The three protonation states of iminodiacetic acids.</p> Full article ">Scheme 4
<p>Suggested complexation reaction of ligand <b>2</b> with Gd(III) ion results in the release of protons.</p> Full article ">Scheme 5
<p>Suggested dynamic formation of aquacomplex of ligand <b>2</b>/Gd(III) complex with water (pH &lt; ~7.5).</p> Full article ">

Figure 1
<p>Experimental angular dependence of Ce-fluorescence yield from 20 mM aqueous solution of Ce(NO₃)₃ · 6H₂O salts (squares). The dashed line represents the calculated angular dependence of the film, in which metal ions are distributed in a layer 10 Å thick at the air/liquid interface. The energy of the incident beam was 13.6 keV.</p> Full article ">Figure 2
<p>Dependence of <span class="html-italic">Ln</span>-O distance (R, Å) from central atom type. Red and green curves are used to plot data for solutions and solids, respectively. The red arrow indicates a “break” in the interatomic distances at Yb.</p> Full article ">Figure 3
<p>(<b>a</b>) Average <span class="html-italic">Ln</span>-O interatomic distances (R, Å) in the structures of <span class="html-italic">Ln</span>(NO₃)₃ · <span class="html-italic">x</span>H₂O salts, according to literature data highlighting the (<b>b</b>) Sm-Dy, (<b>c</b>) Dy-Yb regions. Red dots: interatomic distances calculated from phase analysis of the commercial samples we studied.</p> Full article ">Figure 4
<p>Diffraction patterns of water and solutions with c = 50 mM and c = 134 mM: <span class="html-italic">Ln</span>(NO₃)₃ · <span class="html-italic">x</span>H₂O with (<b>a</b>) <span class="html-italic">Ln</span> = Ce, (<b>b</b>) Sm, (<b>c</b>) Gd, (<b>d</b>) Tb, (<b>e</b>) Yb.</p> Full article ">Figure 5
<p>(<b>a</b>) FT-IR spectra of <span class="html-italic">Ln</span>(NO₃)₃ · <span class="html-italic">x</span>H₂O solutions (<span class="html-italic">Ln</span> = Ce, Sm, Gd, Yb); (<b>c</b>) part of the spectrum (1200–1500 cm⁻¹) of Yb(NO₃)₃ · xH₂O solution (c = 50 mM and 100 mM); ((<b>b</b>,<b>d</b>,<b>e</b>) for c = 20 mM) spectrum sections.</p> Full article ">Figure 5 Cont.
<p>(<b>a</b>) FT-IR spectra of <span class="html-italic">Ln</span>(NO₃)₃ · <span class="html-italic">x</span>H₂O solutions (<span class="html-italic">Ln</span> = Ce, Sm, Gd, Yb); (<b>c</b>) part of the spectrum (1200–1500 cm⁻¹) of Yb(NO₃)₃ · xH₂O solution (c = 50 mM and 100 mM); ((<b>b</b>,<b>d</b>,<b>e</b>) for c = 20 mM) spectrum sections.</p> Full article ">Figure 6
<p>Relationship between the pH value and the concentration of <span class="html-italic">Ln</span>(NO₃)₃ · <span class="html-italic">x</span>H₂O solution with (<b>a</b>) <span class="html-italic">x</span> = 6 for <span class="html-italic">Ln</span> = Ce, Sm, Gd and <span class="html-italic">x</span> is unknown for Yb; (<b>b</b>) <span class="html-italic">x</span> = 6 for <span class="html-italic">Ln</span> = Ce, Sm, Tb, Gd and <span class="html-italic">x</span> is unknown for Yb (pH measurement error is ±0.03).</p> Full article ">Figure 7
<p>Relationship between the growth inhibition zone (D, mm) and (<b>a</b>) concentration (c, mM) and (<b>b</b>) pH of <span class="html-italic">Ln</span>(NO₃)₃ · <span class="html-italic">x</span>H₂O solutions (<span class="html-italic">Ln</span> = Ce, Sm, Gd, Tb, Yb). Convergence of results based on three independent measurements; D ± 0.02 mm.</p> Full article ">

Figure 1
<p>Distribution diagram for L-malic acid.</p> Full article ">Figure 2
<p>Distribution diagram for the equimolar systems studied: (<b>a</b>) La(III)/L-malic acid; (<b>b</b>) Nd(III)/L-malic acid; (<b>c</b>) Gd(III)/L-malic acid; (<b>d</b>) Tb(III)/L-malic acid; (<b>e</b>) Ho(III)/L-malic acid; (<b>f</b>) and Lu(III)/L-malic acid.</p> Full article ">Figure 3
<p>Distribution diagram for the systems studied with excess of L-malic acid: (<b>a</b>) La(III)/L-malic acid; (<b>b</b>) Nd(III)/L-malic acid; (<b>c</b>) Gd(III)/L-malic acid; (<b>d</b>) Tb(III)/L-malic acid; (<b>e</b>) Ho(III)/L-malic acid; and (<b>f</b>) Lu(III)/L-malic acid.</p> Full article ">Figure 4
<p>Possible configurations of L-malic acid with lanthanide ions in formed complexes.</p> Full article ">Figure 5
<p>Emission spectra of the systems: (<b>a</b>) Tb(III)/L-malic acid (1:1 ratio); (<b>b</b>) Tb(III)/L-malic acid (1:2 ratio).</p> Full article ">Figure 6
<p>IR spectra for the equimolar systems studied: (<b>a</b>) La(III)/L-malic acid; (<b>b</b>) Nd(III)/L-malic acid; (<b>c</b>) Gd(III)/L-malic acid; (<b>d</b>) Tb(III)/L-malic acid; (<b>e</b>) Ho(III)/L-malic acid; and (<b>f</b>) Lu(III)/L-malic acid.</p> Full article ">Figure 7
<p>IR spectra for the systems studied with excess of L-malic acid: (<b>a</b>) La(III)/L-malic acid; (<b>b</b>) Nd(III)/L-malic acid; (<b>c</b>) Gd(III)/L-malic acid; (<b>d</b>) Tb(III)/L-malic acid; (<b>e</b>) Ho(III)/L-malic acid; and (<b>f</b>) Lu(III)/L-malic acid.</p> Full article ">Figure 8
<p>The CD spectra of the 1:1 systems: (<b>a</b>) La/Mal at pH 3.0, 6.3, and 8.9; (<b>b</b>) Ho/Mal at pH 4.3, 6.2, 7.7, and 10.2.</p> Full article ">Figure 9
<p>The CD spectra of the 1:2 systems: (<b>a</b>) La/Mal at pH 2.5, 6.3, and 9.2; (<b>b</b>) Ho/Mal at pH 4.4, 6.3, and 8.0.</p> Full article ">

Figure 1
<p>ATR-IR spectra of heterodinuclear [Ln(hfac)₃Co(acac)₃] (<b>1Ln</b>) complexes: Ln = La, (black); Pr, (blue); Sm, (green) and Dy (orange).</p> Full article ">Figure 2
<p>The ¹H (<b>left</b>) and ¹⁹F (<b>right</b>) NMR of [La(hfac)₃Co(acac)₃], <b>1La</b>.</p> Full article ">Figure 3
<p>ATR-IR spectra of [(Ln(hfac)₃)₂Co(acac)₃] (<b>2Ln</b>): La, (black); Pr, (blue); Sm, (green), Dy, (red).</p> Full article ">Figure 4
<p>ATR-IR spectra of [(La(hfac)₃)₂Co(acac)₃] (black) and [La(hfac)₃Co(acac)₃] (blue).</p> Full article ">Figure 5
<p>ATR-IR in the range of 1700–1350 cm⁻¹: (i) [(La(hfac)₃)₂Co(acac)₃] (black); (ii) [(La(hfac)₃)₂Co(acac)₃] after 1 h air exposure (blue); (iii) [La(hfac)₃Co(acac)₃] (green). Bands increasing (green *) or decreasing (black *) with time are marked.</p> Full article ">Figure 6
<p>The ¹H (<b>left</b>) and ¹⁹F (<b>right</b>) NMR spectra of [(La(hfac)₃)₂Co(acac)₃] in CDCl₃.</p> Full article ">Figure 7
<p>The ¹H and ¹⁹F NMR spectra of [(La(hfac)₃)₂Co(acac)₃] in CDCl₃: (i) immediately after preparation (black) and (ii) after a few days (brown).</p> Full article ">Figure 8
<p>Optimized structure of [(La(hfac)₃)₂Co(acac)₃] (<b>2La</b>). The green, grey, cyan, red and violet spheres are F, C, La, O and Co atoms, respectively. H atoms are omitted for clarity. Level of theory: PBE def2/JK, DFT-D3.</p> Full article ">Figure 9
<p>The stability trend, as ∆G values, for the dinuclear [Ln(hfac)₃Co(acac)₃] and trinuclear [(Ln(hfac)₃)₂Co(acac)₃] complexes (Ln = La, Pr and Sm). All values are in kcal/mol.</p> Full article ">Figure 10
<p>(<b>Left</b>): ATR-IR of [La(hfac)₃Ru(acac)₃] (black) and [La(hfac)₃Co(acac)₃] (blue). (<b>Right</b>): ATR-IR of [(La(hfac)₃)₂Ru(acac)₃] (black) and [La(hfac)₃Ru(acac)₃] (blue).</p> Full article ">Figure 11
<p>ATR-IR of (i) [(La(hfac)₃)₂Ru(acac)₃] (black); (ii) after 4′ of air exposure (blue); (iii) after 30′ (green) and [La(hfac)₃Ru(acac)₃] (red). Bands increasing (red *) or decreasing (black *) with time are marked.</p> Full article ">Figure 12
<p>Numbering of ¹H NMR protons in [Ln(hfac)₃M(acac)₃].</p> Full article ">Figure 13
<p>Numbering of ¹H NMR protons in [(La(hfac)₃)₂Co(acac)₃].</p> Full article ">Scheme 1
<p>Heterodinuclear metal complex formation, exemplified here for a formally unsaturated [Ln(hfac)₃] and [M(acac)₃] with the metal M in an octahedral <span class="html-italic">tris</span>-chelate environment.</p> Full article ">Scheme 2
<p>Heterotrinuclear f-d-f sandwich metal complex formation, exemplified here for Ln = La and M = Co or Ru in an octahedral <span class="html-italic">tris</span>-chelate environment.</p> Full article ">

Figure 1
<p>Absorbance spectra of the four Ru-oligothiophenes (Ru-<b>1</b>, brown; Ru-<b>2</b>, red; Ru-<b>3</b>, green; Ru-<b>4</b>, blue; 0.01 mM in acetonitrile) (Reprinted with permission from [<a href="#B13-molecules-29-03691" class="html-bibr">13</a>], Copyright 2007 American Chemical Society).</p> Full article ">Figure 2
<p>Chemical structures of chalcogenorhodamine dyes <b>18</b>–<b>20</b>.</p> Full article ">Figure 3
<p>Emission spectra of complex Cd₂[OOCC₅H₃NPO₃H]₂·H₂O (<b>28</b>) (<span class="html-italic">λ</span>_ex = 323 nm), Zn[OOCC₅H₄NPO₃]·H₂O (<b>29</b>) (λ_ex = 365 nm) and free ligand <b>27</b> (λ_ex = 521 nm) (reprinted with permission from [<a href="#B28-molecules-29-03691" class="html-bibr">28</a>], Copyright Taylor and Francis Ltd., <a href="http://www.tandfonline.com" target="_blank">http://www.tandfonline.com</a>).</p> Full article ">Figure 4
<p>Chemical structures of iridium complexes <b>39</b>–<b>42</b>.</p> Full article ">Figure 5
<p>Chemical structures of complexes <b>43</b>–<b>45</b>.</p> Full article ">Figure 6
<p>Chemical structures of ligands <b>46</b>–<b>52</b>.</p> Full article ">Figure 7
<p>Chemical structures of <span class="html-italic">N,O</span>-donor <span class="html-italic">N</span>-heterocyclic aromatic diphosphonate ligands <b>53</b>–<b>55</b>.</p> Full article ">Figure 8
<p>Chemical structures of ligands <b>56</b>–<b>58</b>.</p> Full article ">Figure 9
<p>Chemical structures of ruthenium complexes <b>59</b>–<b>61</b>.</p> Full article ">Figure 10
<p>Chemical structures of complexes <b>65</b>–<b>68</b>.</p> Full article ">Figure 11
<p>Chemical structures of iridium(III) complexes <b>84</b> and <b>85</b>.</p> Full article ">Figure 12
<p>Chemical structures of platinum complexes <b>86</b> and <b>87</b>.</p> Full article ">Figure 13
<p>Chemical structures of ligands <b>91</b>–<b>94</b> and equilibrium <b>A</b>–<b>D</b> of <b>92</b> at different pH.</p> Full article ">Figure 14
<p>Chemical structures of complexes <b>95</b>–<b>97</b>.</p> Full article ">Figure 15
<p>Chemical structures of the sensitizer/donor <b>106</b> and the dyad <b>107</b>/<b>108</b>.</p> Full article ">Figure 16
<p>Proposed electron fluxes in the illuminated heterotriad <b>106</b>|TiO₂ on SnO₂ (Reprinted with permission from [<a href="#B53-molecules-29-03691" class="html-bibr">53</a>]).</p> Full article ">Figure 17
<p>Chemical structure of complex <b>112</b>.</p> Full article ">Figure 18
<p>Chemical structure of 2-pyrazinephosphonic acid <b>113</b>.</p> Full article ">Figure 19
<p>Chemical structures of pyrazine-functionalized calix [<a href="#B4-molecules-29-03691" class="html-bibr">4</a>]arene ligands <b>117</b>–<b>119</b>, and a schematic presentation of metal co-ordination.</p> Full article ">Figure 20
<p>Absorption spectra of ligands <b>117</b>–<b>119</b> in BumimTf₂N (conc.: 0.25 mmol/L at 25 °C) (reprinted with permission from [<a href="#B58-molecules-29-03691" class="html-bibr">58</a>], Copyright The Royal Society of Chemistry 2015).</p> Full article ">Figure 21
<p>Chemical structures of TBCA (<b>123</b>) and TPCA (<b>124</b>).</p> Full article ">Figure 22
<p>Device configuration of multilayer PLEDs and molecular structures of used materials (GPF—green-emitting polyfluorene; PEDOT:PSS—poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate); ETL—electron-transporting layer; EML—emitting layer; ITO—indium tin oxide) (Used with permission of The Royal Society of Chemistry, from [<a href="#B63-molecules-29-03691" class="html-bibr">63</a>], Copyright 2016; permission conveyed through Copyright Clearance Center, Inc.).</p> Full article ">Scheme 1
<p>Synthesis of bithiophenes and tetrathiophenes <b>1</b>–<b>4</b>.</p> Full article ">Scheme 2
<p>Synthesis of chalcogenophosphonato-substituted bithiophenes. Reagents and conditions: (i) 2,2′-biphenol or 2,2-dimethyl-1,3-propanediol, toluene, reflux; (ii) (a) BuLi, −78 °C, THF; (b) Ph₂PCl, 0 °C—rt, 2 h; (iii) (X = O) H₂O₂·urea complex or N(O)Me₃; (X = S) S₈; (X = Se) Se powder, DCM, rt.</p> Full article ">Scheme 3
<p>Synthesis of bis(aryl- and heteroaryl)phosphonic acids <b>13</b>–<b>17</b>.</p> Full article ">Scheme 4
<p>The synthesis of compound <b>18</b>.</p> Full article ">Scheme 5
<p>Synthesis of the ligand <b>30</b>.</p> Full article ">Scheme 6
<p>Synthesis of ligands <b>31</b> and <b>32</b>.</p> Full article ">Scheme 7
<p>Synthetic protocol for the preparation of ligands <b>35</b> and <b>36</b>.</p> Full article ">Scheme 8
<p>Synthesis of iridium complex <b>38</b> from complex <b>37</b>.</p> Full article ">Scheme 9
<p>Synthesis of the complex <b>63</b>.</p> Full article ">Scheme 10
<p>Synthesis of complex <b>64</b>.</p> Full article ">Scheme 11
<p>General synthesis of ligands <b>72</b>.</p> Full article ">Scheme 12
<p>Synthesis and spectroscopic data of complexes <b>73</b>–<b>80</b> (absorption maximum measured in 0.1 N sulfuric acid; emission maximum measured for the anionic forms of the complexes at room temperature in deaerated methanol; emission lifetimes for the anionic forms of the complexes).</p> Full article ">Scheme 13
<p>Synthesis of complex <b>82</b>.</p> Full article ">Scheme 14
<p>Synthesis of the dimer <b>83</b> and the regeneration of complex <b>82</b>.</p> Full article ">Scheme 15
<p>Synthesis and chemical structures of phosphonates <b>88</b>–<b>90</b>.</p> Full article ">Scheme 16
<p>The synthesis of terpyridyl ligand <b>99</b> for the identification of ions Fe(II), Fe(III), Ru(III) and Zn(II) in dilute aqueous solutions.</p> Full article ">Scheme 17
<p>Synthetic strategies for the synthesis of Ru complex <b>104</b>.</p> Full article ">Scheme 18
<p>Synthesis of complex sensitizer/donor type <b>105</b>.</p> Full article ">Scheme 19
<p>Synthesis of complex <b>110</b>.</p> Full article ">Scheme 20
<p>Synthesis of the phosphopyrazole <b>120</b> and the pyridyl amino amide <b>121</b>.</p> Full article ">Scheme 21
<p>Synthesis of the aminophenoxazinone <b>122</b>.</p> Full article ">Scheme 22
<p>Synthesis of phosphonate <b>127</b> (TPPO).</p> Full article ">

Figure 1
<p>Distribution diagram of the hydrolytic species of the Ce³⁺ ion at 1.0 mM [Ce³⁺].</p> Full article ">Figure 2
<p>Distribution diagram of 1.0 mM Ce³⁺ in the presence of 3.0 mM total phosphate and 40.0 mM total citrate up to pH 7.36, when the formation of solid CePO₄ is observed.</p> Full article ">Figure 3
<p>White fluffy cloud precipitate observable in the test-tubes at 1.0 mM of Ce³⁺ in CD, DF, and DM culture media.</p> Full article ">Figure 4
<p>Bacterial cultivation on different agarized culture media after 48 h of incubation.</p> Full article ">Figure 5
<p>Fungi cultivation and growth on different agarized culture media after 5 days of incubation.</p> Full article ">Figure 6
<p>Growth curve of <span class="html-italic">B. stratosphericus</span> in MCML and Davis and Mingioli (DM) media.</p> Full article ">Figure 7
<p>Growth curve of <span class="html-italic">D. hansenii</span> in MCML and Czapek Dox (CD) media.</p> Full article ">Figure 8
<p>Ln³⁺ accumulation capability of <span class="html-italic">B. stratosphericus</span>, expressed as μg · mg⁻¹ of dry weight.</p> Full article ">

Figure 1
<p>Liquid chromatograms of the reactions of different equivalents of acid anhydride with peptides.</p> Full article ">Figure 2
<p>Histidine site number.</p> Full article ">Figure 3
<p>Spectrum of ¹H NMR spectrum of raw peptides.</p> Full article ">Figure 4
<p>Spectrum of ¹H-¹³C HSQC NMR spectrum of raw peptides.</p> Full article ">Figure 5
<p>Spectrum of ¹H-¹H COSY NMR spectrum of raw peptides.</p> Full article ">Figure 6
<p>Spectrum of ¹H-¹³C HMBC NMR spectrum of raw peptides.</p> Full article ">Figure 7
<p>Spectrum of ¹³C-NMR spectrum of raw peptides.</p> Full article ">Figure 8
<p>Chemical shifts of important structures in raw polypeptides.</p> Full article ">Figure 9
<p>Coupling functional group label.</p> Full article ">Figure 10
<p>Spectrum of ¹H-NMR spectrum of peptide product coupled to an anhydride molecule.</p> Full article ">Figure 11
<p>Spectrum of ¹H-¹³C HSQC NMR spectrum of peptide product coupled to an anhydride molecule.</p> Full article ">Figure 12
<p>Spectrum of ¹H-¹³C HMBC NMR spectrum of peptide product coupled to an anhydride molecule.</p> Full article ">Figure 13
<p>Spectrum of ¹H-¹HCOSY NMR spectrum of peptide product coupled to an anhydride molecule.</p> Full article ">Figure 14
<p>Spectrum of ¹³C-NMR spectrum of peptide product coupled to an anhydride molecule.</p> Full article ">Figure 15
<p>The chemical shift values of important structures in peptide products coupled with an anhydride molecule.</p> Full article ">Figure 16
<p>The structure of the polypeptide with associated equations.</p> Full article ">

Graphical abstract
Full article ">Figure 1
<p>(<b>a</b>) Coordination environment of the Eu^III cations in complex <b>4</b>. (<b>b</b>) The one-dimensional ring-chain structure of complex <b>4</b>. (<b>c</b>) Two-dimensional supramolecular structure of complex <b>4</b>.</p> Full article ">Figure 1 Cont.
<p>(<b>a</b>) Coordination environment of the Eu^III cations in complex <b>4</b>. (<b>b</b>) The one-dimensional ring-chain structure of complex <b>4</b>. (<b>c</b>) Two-dimensional supramolecular structure of complex <b>4</b>.</p> Full article ">Figure 2
<p>(<b>a</b>) Emission spectra of complex <b>4</b>. (<b>b</b>) Emission spectra of complex <b>3</b>. (<b>c</b>) Emission spectra of complex <b>6</b>.</p> Full article ">Figure 3
<p>(<b>a</b>) Luminescence decay curves of complex <b>4</b>. (<b>b</b>) Luminescence decay curves of complex <b>3</b>.</p> Full article ">Figure 4
<p>CIE chromaticity diagrams for complex <b>4</b> and <b>3</b>.</p> Full article ">Figure 5
<p>(<b>a</b>) Emission spectra of complex <b>4</b> in diverse metal ions. (<b>b</b>) Comparisons for intensities of complex <b>4</b> in different metal ions. (<b>c</b>,<b>e</b>) Luminescence quenching of complex <b>4</b> dispersed in DMF with gradual addition of Cu²⁺ and Co²⁺ ions, respectively. (<b>d</b>,<b>f</b>) The fitting of the fluorescence change value of complex <b>4</b> in Cu²⁺ and Co²⁺ ions, respectively.</p> Full article ">Figure 6
<p>(<b>a</b>) Emission spectra of complex <b>3</b> in diverse metal ions. (<b>b</b>) Comparisons for intensities of complex <b>3</b> in different metal ions. (<b>c</b>) Luminescence quenching of complex <b>3</b> dispersed in DMF with gradual addition of Cu²⁺ ion. (<b>d</b>) The fitting of the fluorescence change value of complex <b>3</b> in Cu²⁺ ion.</p> Full article ">Figure 7
<p>(<b>a</b>) Emission spectra of complex <b>4</b> in diverse analytes. (<b>b</b>) Comparisons for intensities of <b>4</b> in diverse analytes. (<b>c</b>) Emission spectra of complex <b>4</b> in CH₃CN with different concentrations of NB.</p> Full article ">Figure 8
<p>(<b>a</b>) Emission spectra of complex <b>3</b> in diverse analytes. (<b>b</b>) Comparisons for intensities of <b>3</b> in diverse analytes. (<b>c</b>) Emission spectra of complex <b>3</b> in DMF with different concentrations of NB.</p> Full article ">Figure 9
<p>HOMO and LUMO energy levels of ligand and the selected analytes.</p> Full article ">Figure 10
<p>Hirshfeld surface mapped with dnorm (<b>left</b>), shape index (<b>middle</b>), and curvedness (<b>right</b>) for complex <b>4</b>.</p> Full article ">Figure 11
<p>Two-dimensional (2D) fingerprint plots of Hirshfeld surfaces for complex <b>4</b>.</p> Full article ">Scheme 1
<p>Coordination modes of the (cpt)⁻ ligand. (<b>a</b>) a bidentate coordination fashion (<b>b</b>) a tridentate coordination fashion.</p> Full article ">

Figure 1
<p>Schematic representation of the four Ln(III) complexes where R corresponds to methyl (A-complex); 1,2,3-triazole-4- (B-complex); 2-(4-chlorophenyl)-2<span class="html-italic">H</span>-1,2,3-triazole-4- (C-complex); and 2-(4-chlorophenyl)-5-(pyrrolidin-1-yl)-2<span class="html-italic">H</span>-1,2,3-triazole-4- (2b′ ligand) (Ln(2b′)₃ complex).</p> Full article ">Figure 2
<p>Two conformations found by rotation around the carboxylate group. The italics numbers in green color corresponds to the three 2b′ ligands of the complex.</p> Full article ">Figure 3
<p>Optimized structure of the La(2b′)₃ complex by the CAM-B3LYP method and the Lanl2dz and Cep-4g basis set.</p> Full article ">Figure 4
<p>Labeling of the atoms in the 2b′ ligand of the complex.</p> Full article ">Figure 5
<p>Relationships are established with the bond lengths and angles: (<b>a</b>,<b>b</b>) Between the Ln-O12 and C11-O12 bond lengths by CAM-B3LYP and M06-2X methods. (<b>c</b>) Between the Lanthanide charge and Ln-O12 bond length. (<b>d</b>) Between lanthanide charge and C11-O12 bond length. (<b>e</b>) Between lanthanide charge and C9-C11 bond length. (<b>f</b>) Between the O12-Ln-O13 angle and dipole moment of the complex.</p> Full article ">Figure 6
<p>Relationships established with the atomic charges: (<b>a</b>,<b>b</b>) Between lanthanide charge and charge on O12 by CAM-B3LYP and M06-2X. (<b>c</b>) Between the lanthanide charge and charge on the C11 atom. (<b>d</b>) Between lanthanide charge and C9 charge. (<b>e</b>) Between the lanthanide charge and dipole moment of the complex. (<b>f</b>) Between the atomic charge on O12 and the dipole moment of the complex.</p> Full article ">Figure 7
<p>Relationships established at the M06-2X level with the molecular properties: (<b>a</b>) Between lanthanide charge and HOMO energy. (<b>b</b>) Between the charge on O12 and LUMO energy. (<b>c</b>,<b>d</b>) Between the LUMO-HOMO energy and the lanthanide/O12 charges, respectively. (<b>e</b>,<b>f</b>) Between lanthanide charge and capacity at constant volume in all complexes and in Ln(2b′)₃ complex, respectively.</p> Full article ">Figure 8
<p>Comparison of the experimental IR spectra of the Ln(2b′)₃ complexes with Ln = La, Ce, Pr, Nd, Sm, Gd, Dy, Ho and Er in the 3750–400 cm⁻¹ range.</p> Full article ">Figure 9
<p>Comparison of the experimental Raman spectra of the Ln(2b′)₃ complexes with Ln = La, Ce, Pr, Nd, Sm, Gd, Dy, Ho and Er in the 2000–50 cm⁻¹ range.</p> Full article ">Figure 10
<p>Impact of the ligand 2b′ and the various Ln(2b′)₃ complexes on (<b>a</b>) the DPPH and (<b>b</b>) ABTS in vitro model systems. Data = mean ± stdev, N = 4.</p> Full article ">

Figure 1
<p>The structure of Sm-OC.</p> Full article ">Figure 2
<p>Substrate scope for the aerobic oxidation of thiols. <span class="html-italic">^a</span> Conditions: Sm-OC (1.15 mol%) were added to a solution of thiols (0.300 mmol, 1.00 equiv.) in AcOEt (8.00 mL) under O₂ balloon at 70 °C and stirred for a duration of 16 h. <span class="html-italic">^b</span> Sm-OC (2.30 mol%) were added to a solution of thiols (0.300 mmol, 1.00 equiv.) in AcOEt (8.00 mL) under O₂ balloon at 70 °C and stirred for a duration of 16 h. <span class="html-italic">^c</span> Sm-OC (2.30 mol%) were added to a solution of thiols (0.300 mmol, 1.00 equiv.) and (3<span class="html-italic">s</span>,5<span class="html-italic">s</span>,7<span class="html-italic">s</span>)-adamantane-1-thiol (0.900 mmol, 3.00 equiv.) in AcOEt (8.00 mL) under O₂ balloon at 70 °C and stirred for a duration of 16 h.</p> Full article ">