Two lanthanide coordination polymers, [Eu(HL)(L)(H2O)2]n(1) and [Tb(H0.5L)2]n(2), based on bifunctional 5-(1H-imidazol-1-yl) isophthalic acid(H2L), are hydrothermally synthesized and characterized by b...Two lanthanide coordination polymers, [Eu(HL)(L)(H2O)2]n(1) and [Tb(H0.5L)2]n(2), based on bifunctional 5-(1H-imidazol-1-yl) isophthalic acid(H2L), are hydrothermally synthesized and characterized by both single-crystal and powder X-ray diffraction analyses, and FT-IR. In compound 1, the basic inorganic building unit of the coordination network is the dinuclear [Eu2(COO)6] cluster. Each [Eu2(COO)6] cluster connects four HL^- ligands and each HLligand links two [Eu2(COO)6] clusters, resulting in a 2D coordination layer. The adjacent 2 D layers are further connected via neighboring inter-layer hydrogen bonds to give a 3D supramolecular structure. In compound 2, the Tb^3+ is coordinated to six oxygen atoms. Each Tb^3+ ion connects six ligands and each ligand links three Tb^3+ ions, leading to a 3D coordination polymeric network which exhibits remarkably high thermal stability up to 500℃. Furthermore, due to the successful incorporation of Tb^3+, compound 2 displays characteristic luminescent emission in the solid state at room temperature. The combination of high thermal stability and fluorescent property of compound 2 would make it as a promising light-emitting material.展开更多
Two coordination polymers, namely [Pb(Hbtc)(phen)]n(1) and {[Cd3(btc)2(H2O)4]·2H2O}n(2, H3btc = biphenyl-2,5,3'-tricarboxylic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray d...Two coordination polymers, namely [Pb(Hbtc)(phen)]n(1) and {[Cd3(btc)2(H2O)4]·2H2O}n(2, H3btc = biphenyl-2,5,3'-tricarboxylic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a zigzag chain 1D coordination network, which is further extended into a 3D supramolecular architecture via O–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 3D open framework based on a tricadmium(II) subunit, generating a trinodal 4,4,6-connected net with the 4,4,6T24 topology defined by the point symbol of(44·62)3(46·69)2. Thermal stability and luminescent properties of both compounds were studied and discussed.展开更多
A novel europium(Ⅲ) coordination polymer, [Eu3(pydc)3(SO4)(H2O)5(ox)0.5]·3H2O(1, H2ox = oxalic acid, H2 pydc = pyridine-2,6-dicarboxylic acid), has been synthesized hydrothermally from the self-assem...A novel europium(Ⅲ) coordination polymer, [Eu3(pydc)3(SO4)(H2O)5(ox)0.5]·3H2O(1, H2ox = oxalic acid, H2 pydc = pyridine-2,6-dicarboxylic acid), has been synthesized hydrothermally from the self-assembly of lanthanide ions(Eu3+) with the flexible oxalic acid and the rigid pyridine-2,6-dicarboxylic acid ligands, respectively. It crystallizes in the triclinic system, space group P1 with a = 11.225(4), b = 12.390(5), c = 13.752(5)A, α = 89.228(7), β = 71.142(6), γ = 75.552(6)°, Dc = 2.317 g/cm^3, μ = 5.480 mm^-1, F(000) = 1150, Z = 2, the final R = 0.0351 and w R = 0.0949 for 8782 observed reflections with I 〉 2σ(I). Structural analysis reveals that complex 1 exhibits a three-dimensional metal-organic framework via π-π stacking interactions. In addition, complex 1 displays a red fluorescence emission in the solid state at room temperature, which corresponds to the 5D0 → 7F2 transition of Eu3+ ions.展开更多
In this work, we synthesized a new two-dimensional Cd(Ⅱ) coordination polymer, [Cd(1,4-NDC)(L)](1), by using mixed 1,4-naphthalenedicarboxylic acid(1,4-H2NDC) and typical chelating N-donor ligands 2-(2-chl...In this work, we synthesized a new two-dimensional Cd(Ⅱ) coordination polymer, [Cd(1,4-NDC)(L)](1), by using mixed 1,4-naphthalenedicarboxylic acid(1,4-H2NDC) and typical chelating N-donor ligands 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline ligand(L). Compound 1 crystallizes in monoclinic, space group P21/n with a = 12.936(5), b = 15.245(5), c = 13.499(5) ?, β = 105.456(5)o, V = 2565.9(16) A^3, Z = 4, C(31)H(16)CdClFN4O4, Mr = 675.33, Dc = 1.748 g/cm^3, F(000) = 1344, μ(MoKa) = 1.011 mm^-1, R = 0.0350 and wR = 0.0926. In 1, each 1,4-NDC anion bridges three adjacent Cd(Ⅱ) atoms to give a two-dimensional layer structure. The L ligands are attached on both sides of the layer in chelating coordination modes. In addition, the N–H···O hydrogen bond between L and 1,4-NDC further stabilizes the layer structure of 1. Moreover, the solid state luminescent property of 1 was also investigated at room temperature.展开更多
A novel Cd(Ⅱ) coordination polymer with diacylhydrazide ligand N,N?-bis(3-methoxysalicyl)-2,6-pyridinedicarbohydrazide(H_6msphz),[Cd_2(H_2msphz)(Py)_4]_n(1,Py = pyridine) has been synthesized through sol...A novel Cd(Ⅱ) coordination polymer with diacylhydrazide ligand N,N?-bis(3-methoxysalicyl)-2,6-pyridinedicarbohydrazide(H_6msphz),[Cd_2(H_2msphz)(Py)_4]_n(1,Py = pyridine) has been synthesized through solvothermal reaction and structurally characterized by single-crystal X-ray diffraction,IR,TGA and PXRD investigations. It crystallizes in triclinic system,space group P1,with a = 11.0230(11),b = 11.7264(15),c = 17.3395(14) ?,α = 70.520(9),β = 84.806(7),γ = 81.965(9)°,V = 2089.9(4) ?~3,Dc = 1.638 gcm^(–3),μ = 1.083 mm^(-1),F(000) = 1032,Z = 2 and S = 1.040. In complex 1,the H_2msphz4-ligand uses not only its coordinated pocket to catch one Cd(Ⅱ) ion,but also its two terminal groups to chelate other two Cd(Ⅱ) ions,leading to the formation of a chain structure. The adjacent chains are further assembled together by two kinds of π-π interactions between the Py rings,resulting in the finial double layered supramolecular structure. In addition,complex 1 is found to show photoluminescence in the solid state at room temperature,which can be ascribed to the intraligand π→π* transitions.展开更多
A new Cd(II) coordination polymer with 2-nitroterephthalie acid (H2npa) and 1,4- bis(2-methyl-imidazol-l-yl) butane (bib) has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray d...A new Cd(II) coordination polymer with 2-nitroterephthalie acid (H2npa) and 1,4- bis(2-methyl-imidazol-l-yl) butane (bib) has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, IR and EA. Complex [Cd(npa)(bib)]n (1) is of orthorhombic system, space group Pcca with a = 16.1750(5), b = 9.8764(5), c = 15.5890(3) A, V = 2490.4(2) A3, Z = 4, Mr = 539.82, Dc = 1.440 g/cm3, F(000) = 1088,μ = 0.918 mm-1, the final R = 0.0320 and wR = 0.0775 for 2253 reflections with I 〉 2σ(I). X-ray diffraction analysis reveals that complex 1 displays a four-fold interpenetrated dia topology. Furthermore, the luminescent property for complex 1 is also investigated in solid state at room temperature.展开更多
Three new supramolecular polymers, [(IP)(H2SO4)(H2O)](1), [(H2SDC)(BPA)](2) and [Mn(SDC)(IP)2]n (3), have been constructed by three modes(rigid IP, rigid SDC + flexible BPA, rigid IP + rigid SDC...Three new supramolecular polymers, [(IP)(H2SO4)(H2O)](1), [(H2SDC)(BPA)](2) and [Mn(SDC)(IP)2]n (3), have been constructed by three modes(rigid IP, rigid SDC + flexible BPA, rigid IP + rigid SDC). Polymers 1 and 2 are supramolecular structures, assembled by hydrogen bonds and π···π interactions. X-ray structure analysis of 3 shows waved 1D chains which form a 3D supramolecular network by hydrogen bonds and π···π interactions. Solid-state properties of thermal stability, luminescent properties, and X-ray powder diffractions for these crystalline materials have also been investigated, and polymer 3 is considered to be a good stable luminescence material.展开更多
Two new Zn~Ⅱ coordination polymers,namely,[Zn L(o-bdc)]n(1) and [Zn L(mbdc)]_n·n H_2O(2)(L = 4?-(3-pyridyl)-3,2?:6?,3??-terpyridine,H_2(o-bdc) = benzene-1,2-dicarboxylic acid,H_2(m-bdc) = be...Two new Zn~Ⅱ coordination polymers,namely,[Zn L(o-bdc)]n(1) and [Zn L(mbdc)]_n·n H_2O(2)(L = 4?-(3-pyridyl)-3,2?:6?,3??-terpyridine,H_2(o-bdc) = benzene-1,2-dicarboxylic acid,H_2(m-bdc) = benzene-1,3-dicarboxylic acid),were synthesized by hydrothermal methods. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic C2/c space group,with a = 28.016(2),b = 11.3815(11),c = 19.8071(17) ?,β = 133.961(2)°,V = 4546.2(7) ?3,Z = 8,Mr = 539.83,Dc = 1.577 Mg/m^3,μ = 1.127 mm-1,F(000) = 2208,the final R = 0.0426 and w R = 0.0986 for 2875 observed reflections with I 〉 2σ(I) and displays a 1D coordination chain. While compound 2 crystallizes in monoclinic C2/c space group,with a = 15.6003(14),b = 11.9152(11),c = 26.633(3) ?,β = 94.320(2)°,V = 4936.5(8) ?~3,Z = 4,M_r = 1115.67,Dc = 1.496 Mg/m^3,μ = 1.043 mm^(-1),F(000) = 2272,the final R = 0.0499 and w R = 0.1342 for 2659 observed reflections with I 〉 2σ(I) and shows a classical 3D cds topological network with point symbol of {65.8}. Furthermore,thermal stability and luminescent properties of 1 and 2 have also been investigated.展开更多
A new 1D copper(Ⅱ) polymer [Cu(Hpt)(3,5-DMBA)]n has been hydrothermally synthesized with copper acetate,3-(pyridin-2-yl)-1,2,4-triazole(Hpt) and 3,5-dimethylbenzoic acid(3,5-DMBA). It crystallizes in tric...A new 1D copper(Ⅱ) polymer [Cu(Hpt)(3,5-DMBA)]n has been hydrothermally synthesized with copper acetate,3-(pyridin-2-yl)-1,2,4-triazole(Hpt) and 3,5-dimethylbenzoic acid(3,5-DMBA). It crystallizes in triclinic space group P1,with a = 8.1974(6),b = 8.3280(6),c = 12.5021(9) ?,α = 84.3320(10),β = 71.8870(10),γ= 65.4560(10)o,V = 737.44(9) ?~3,Dc = 1.612 g/cm3,Z = 2,F(000) = 366,GOOF = 1.035,R = 0.0298 and w R = 0.0855. The crystal structure is a one-dimensional(1-D) chain in which the Cu(Ⅱ) is five-coordinated with square pyramidal geometry. The crystal structure shows that the whole molecule consists of two copper ions bridged by two μ12-η:η0-3,5-dimethylbenzoic acid anions and two 3-(pyridin-2-yl)-1,2,4-triazole molecules. The coordination environment of Cu(Ⅱ) ion is CuO+2N_3. The luminescence and thermal properties of the complex were investigated.展开更多
A novel terbium(III) coordination polymer [Tb(C7H3NO4)(C6H4NO2)(H2O)] was successfully synthesized hydrothermally and characterized by single-crystal X-ray diffraction. The complex is of monoclinic, space group P21/c ...A novel terbium(III) coordination polymer [Tb(C7H3NO4)(C6H4NO2)(H2O)] was successfully synthesized hydrothermally and characterized by single-crystal X-ray diffraction. The complex is of monoclinic, space group P21/c with a = 9.2252(11), b = 14.1477(16), c = 10.5134(12) A, β = 95.770(2)°, V = 1365.2(3) A3, Z = 4, Dc = 2.248 g·cm-3, F(000) = 880, the final R = 0.0176 and w R = 0.0411 for 2149 observed reflections with I 】 2σ(I). The complex is extended into a three-dimensional network structure with 24-atom rings which are composed of Tb, C and O atoms. The complex displays green fluorescence emission in the solid state at room temperature, which corresponds to 5D4 → 7F5 transition of the Tb(III) ion.展开更多
Two coordination polymers, {[Cu3(tci)2(DMAc)3].6DMAc-2H2O}n (1[) and {[Cu3(tci)2(tpt)2(H2O)2]- 2DMAc-2H2O}n (2) (H3tci = tris(2-carboxyethyl)isocyanurate, tpt = 2,4,6-tris(4-pyridyl)-l,3,5-triazine,...Two coordination polymers, {[Cu3(tci)2(DMAc)3].6DMAc-2H2O}n (1[) and {[Cu3(tci)2(tpt)2(H2O)2]- 2DMAc-2H2O}n (2) (H3tci = tris(2-carboxyethyl)isocyanurate, tpt = 2,4,6-tris(4-pyridyl)-l,3,5-triazine, DMAc = N,N-dimethylacetamide), have been constructed under solvothermal conditions. Both polymers were structurally characterized by single crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric (TG) analyses and powder X-ray diffraction (RXPD). 1 shows a (3,4)-connected 2D layer structure comprising Cu2(CO2)4 paddle-wheel units, which are further bridged by C-H.--O interactions to give a 3D supramolecular network. The introduction oftpt produces different framework for 2 that comprises a dinuclear and a mononuclear Cu(II) building units, which are further bridged together by tci3- and tpt ligands to give a 4-connected 2D topological net. Adjacent 2D layers are packed together via C-H...O interactions and π...π stacking interactions to form a 3D supramolecular structure. In addition, the luminescent properties and the solid-state UV-vis spectra of I and 2 were explored. Furthermore, antiferromagnetic exchange interactions were unveiled in the Cu2(COO)4 units of 1. ~ 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.展开更多
A new 1-D coordination polymer [Cd(Hsal)2(bpp)2] 1 was hydrothermally synthesi- zed by self-assembly of the corresponding metal oxide and salicylic acid (H2sal) with exo-bidentate flexible dipyridyl ligand 1,3-...A new 1-D coordination polymer [Cd(Hsal)2(bpp)2] 1 was hydrothermally synthesi- zed by self-assembly of the corresponding metal oxide and salicylic acid (H2sal) with exo-bidentate flexible dipyridyl ligand 1,3-bis(4-pyridyl)propane (bpp). X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic,space group C2/c with a = 18.942(3),b = 12.9309(19),c = 16.504(2) A,β = 120.072(2)°,V = 3498.3(9)A^3,Z = 4,C40H38CdN4O6,Mr = 783.14,Dc = 1.487 g/cm^3,μ = 0.679 mm^-1,F(000) = 1608,R = 0.0619 and wR = 0.1435 for 3153 observed reflections (I 〉 2σ(I)). The most remarkable feature of 1 lies in the 1-D chain by repeating [Cd2(bpp)2] units which consist of a 24-membered macrocyclic ring. The 1-D motifs are further connected by C–H… O hydrogen bonds to generate a 2-D structure. In addition,thermal stability and luminescent property of compound 1 were also documented.展开更多
A new Pb(Ⅱ) coordination polymer, [Pb(1,4-chdc)(L)]_n·nH_2O(1), was synthesized under hydrothermal condition(1,4-H2 chdc = 1,4-cyclohexanedicarboxylic acid and L = 2-(3-fluorophenyl)-1H-imidazo[4,5-f]...A new Pb(Ⅱ) coordination polymer, [Pb(1,4-chdc)(L)]_n·nH_2O(1), was synthesized under hydrothermal condition(1,4-H2 chdc = 1,4-cyclohexanedicarboxylic acid and L = 2-(3-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline). Its crystal structure was determined by singlecrystal X-ray diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 9.1182(8), b = 11.3249(10), c = 12.7326(12) A, α = 77.897(2), β = 81.644(2), γ = 84.491(2)°, V = 1269.0(2) A^3, Z = 2, C_(27)H_(24)FN_4O_5Pb, M_r = 710.69, D_c = 1.860 g/cm^3, F(000) = 690, μ(MoKa) = 6.701 mm^(-1), R = 0.0349 and wR = 0.0746. In 1, each 1,4-chdc anion bridges two neighboring Pb(Ⅱ) atoms in a bidentate chelating coordination mode to give a chain structure. The L ligands are attached on one side of the chain through chelating the Pb(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. The O-H···O and N-H···O hydrogen bonding interactions further stabilize the supramolecular layer structure of 1. Moreover, solid state luminescent property of 1 was also studied.展开更多
A new complex [Zn(4-nph)(bib)](2n)·nH2O(1) has been obtained by the reaction of metal(Zn(Ⅱ)),1,4-bis(imidazol-1-yl)-butane(bib) with 4-nitrophthalic acid(4-H(2nph)).The crystal structure of 1...A new complex [Zn(4-nph)(bib)](2n)·nH2O(1) has been obtained by the reaction of metal(Zn(Ⅱ)),1,4-bis(imidazol-1-yl)-butane(bib) with 4-nitrophthalic acid(4-H(2nph)).The crystal structure of 1 has been determined by single-crystal X-ray diffraction analysis.Compound 1 is of triclinic system,space group P1 with a = 10.3251,b = 12.4503,c = 16.6497 A,α = 88.487(3),β = 72.529(3),γ = 79.991(3)°,V = 2009.8(5)A^3 and Mr = 945.47.Complex 1 shows a three-dimensional(3 D) framework.Moreover,through intermolecular hydrogen bonds,compound 1 is assembled into a supramolecular structure.The thermal stability and luminescent properties of 1 are also investigated.展开更多
One new chiral metal-organic coordination polymer,[Cd2(dpb)(H2hfipbb)2]n,was obtained under hydrothermal conditions of 1,3-di(pyridineyl)benzene(dpb) and 4,4'-(hexafluoroisopropylidene)bis(benzoic acid)(...One new chiral metal-organic coordination polymer,[Cd2(dpb)(H2hfipbb)2]n,was obtained under hydrothermal conditions of 1,3-di(pyridineyl)benzene(dpb) and 4,4'-(hexafluoroisopropylidene)bis(benzoic acid)(H2hfipbb). The title compound reveals a three-dimensional(3D) framework with two types of helical chains [Cd(COO)]n,which are linked each other to further form a double helical chain [Cd2(COO)2]n by sharing the same Cd(Ⅱ) ions. The dpb connects the double helical chains to generate a 3D framework. These unique structures were studied by single-crystal X-ray and other spectroscopy techniques. In addition,the luminescent,fluorescence lifetime and second harmonic generation efficiency properties in the solid state have been studied.展开更多
A new Cd(Ⅱ) coordination polymer,{[Cd(pda)(bimb)]·(H2O)(0.5)}n(1,H2pda=1,3-phenylenediacetic acid,bimb = 4,4-bis(1-imidazolyl)biphenyl),has been synthesized and characterized by elemental analysis,...A new Cd(Ⅱ) coordination polymer,{[Cd(pda)(bimb)]·(H2O)(0.5)}n(1,H2pda=1,3-phenylenediacetic acid,bimb = 4,4-bis(1-imidazolyl)biphenyl),has been synthesized and characterized by elemental analysis,IR spectroscopy,powder X-ray diffraction(PXRD) analyses and single-crystal X-ray diffraction techniques. Complex 1 shows a 4-connected two-fold interpenetrated three-dimensional(3-D) cds topology. In additional,photoluminescent properties of 1 and its dehydrated product have also been studied.展开更多
A new 1D Cd(II) coordination polymer, [Cd(H2biim)2(SO4)]n·3n H2O(1, H2 biim = 2,2’-H2biimidazole), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in mo...A new 1D Cd(II) coordination polymer, [Cd(H2biim)2(SO4)]n·3n H2O(1, H2 biim = 2,2’-H2biimidazole), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 6.8405(14), b = 17.792(4), c = 14.987(3) A, β = 92.68(3), V = 1822.1(6) A3, Z = 4, C12H18 Cd N8O7S, Mr = 530.80, Dc = 1.935 g/cm3, F(000) = 1064, μ(Mo Ka) = 1.371 mm-1, R = 0.0280 and w R = 0.0617. In 1, adjacent Cd(II) atoms are bridged by sulfate anions in bidentate modes to yield a 1D chain. H2 biim ligands are located on both sides of the chain in chelating bidentate modes. Further, the H2 biim ligands from neighboring chains are paired through π-π interactions to generate a supramolecular layer, which is stabilized by the complicated N–H···O and O–H···O hydrogen bonds. In addition, thermal behavior and luminescent property of 1 have been investigated.展开更多
It is found that the fluorescence of aliphatic poly(amido amine)s including linear and hyperbranched ones can be dramatically enhanced by simple aggregation of polymer chains, attributing to the formation of a varie...It is found that the fluorescence of aliphatic poly(amido amine)s including linear and hyperbranched ones can be dramatically enhanced by simple aggregation of polymer chains, attributing to the formation of a variety of intra- and interchain clusters with shared lone-pair electrons and the restriction of intramolecular motions. Thanks to the combination of strong solid fluorescence and excellent biocompatibility, these non-conjugated polymers become promising candidates for bioimaging such as bacterial detection. This finding not only extends the aggregation-induced emission(AIE) systems from conjugated compounds to non-conjugated materials, which expands the bioapplication range of AIE systems, but also sheds light on the exploration of novel unconventional luminogens.展开更多
A novel photonic composite film based on a luminescent dicyanodistyrylbenzene-based liquid crystal polymer network(LCN) was fabricated by using a silica colloidal crystal as a template. The upper part of inverse opa...A novel photonic composite film based on a luminescent dicyanodistyrylbenzene-based liquid crystal polymer network(LCN) was fabricated by using a silica colloidal crystal as a template. The upper part of inverse opal structure and the luminescence characteristics of dicyanodistyrylbenzene-based moiety endowed the resulting bilayer photonic film with structural color arising from coherent Bragg reflection and fluorescence properties, respectively. A fluorescence enhancement phenomenon was observed in the photonic film due to the overlap between the reflection band and emission band of the fluorescent LCN. More importantly, the photo-induced irreversible Z/E photoisomerization of dicyanodistyrylbenzene-based moiety in the photonic film led to both a reflection spectral shift and an observable fluorescence variation. On the basis of this effective phototuning process, microscopic patterning of photonic film was developed under both fluorescence mode and reflection mode. The work demonstrated here provides a new route to construct photo-responsive photonic film.展开更多
Why many luminescent liquid crystalline polymers(LLCPs)containing aggregation-induced emission luminogen(AIEgen)show weak emission is a question still to be answered.Herein,a series of LLCPs(α-Pns,n=4,8,and 12)with p...Why many luminescent liquid crystalline polymers(LLCPs)containing aggregation-induced emission luminogen(AIEgen)show weak emission is a question still to be answered.Herein,a series of LLCPs(α-Pns,n=4,8,and 12)with polynorbornene as main chain and twoα-dicyanodistyrylbenzene(α-DCS)as side chain are successfully synthesized to solve this issue.Differential scanning calorimetry(DSC),polarized light microscopy(PLM),one-dimentional(1D),two-dimentional(2D)middle-angle and wide-angle X-ray scattering(MAXS and WAXS)results demonstrate that the polymers form smectic A(SmA)phase with the side chains interdigitated packed within the smectic layers.Meanwhile,the photophysical properties ofα-Pns were investigated by ultraviolet-visible(UV-vis)absorption,steady state and time-resolved spectroscopy,and photothermal effect.Results show that the polymers are AIE active,but emit weak emission.The emission peak ofα-Pns film red-shift from 473 to 531 nm,the quantum yield gradually increases from around 1.6%to 14.7%,and the photothermal conversion efficiency decreases from 39%to 19%with the alkyl tail length increased.The photothermal effect,but not photoluminescence,dominates the excited state relaxation.展开更多
基金Financially supported by the Natural Science Foundation of Shandong Province(ZR2014BQ035)the National Natural Science Foundation of China(21501086,21671093)+3 种基金the Tai-Shan Scholar Research Fund of Shandong ProvinceLiaocheng University and college students’ innovative training program(201410447009,201410447010)the financial supports from Liaocheng University(318051401)the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry
文摘Two lanthanide coordination polymers, [Eu(HL)(L)(H2O)2]n(1) and [Tb(H0.5L)2]n(2), based on bifunctional 5-(1H-imidazol-1-yl) isophthalic acid(H2L), are hydrothermally synthesized and characterized by both single-crystal and powder X-ray diffraction analyses, and FT-IR. In compound 1, the basic inorganic building unit of the coordination network is the dinuclear [Eu2(COO)6] cluster. Each [Eu2(COO)6] cluster connects four HL^- ligands and each HLligand links two [Eu2(COO)6] clusters, resulting in a 2D coordination layer. The adjacent 2 D layers are further connected via neighboring inter-layer hydrogen bonds to give a 3D supramolecular structure. In compound 2, the Tb^3+ is coordinated to six oxygen atoms. Each Tb^3+ ion connects six ligands and each ligand links three Tb^3+ ions, leading to a 3D coordination polymeric network which exhibits remarkably high thermal stability up to 500℃. Furthermore, due to the successful incorporation of Tb^3+, compound 2 displays characteristic luminescent emission in the solid state at room temperature. The combination of high thermal stability and fluorescent property of compound 2 would make it as a promising light-emitting material.
基金Funded by the National Natural Science Foundation of Shanxi Province(No.2013011011-6)the Subject Team of Taiyuan University of Science and Technology
文摘Two coordination polymers, namely [Pb(Hbtc)(phen)]n(1) and {[Cd3(btc)2(H2O)4]·2H2O}n(2, H3btc = biphenyl-2,5,3'-tricarboxylic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a zigzag chain 1D coordination network, which is further extended into a 3D supramolecular architecture via O–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 3D open framework based on a tricadmium(II) subunit, generating a trinodal 4,4,6-connected net with the 4,4,6T24 topology defined by the point symbol of(44·62)3(46·69)2. Thermal stability and luminescent properties of both compounds were studied and discussed.
基金financially supported by Foundation of Fujian Educational Committee(JA14348)the National Natural Science Foundation of China(No.21171037)
文摘A novel europium(Ⅲ) coordination polymer, [Eu3(pydc)3(SO4)(H2O)5(ox)0.5]·3H2O(1, H2ox = oxalic acid, H2 pydc = pyridine-2,6-dicarboxylic acid), has been synthesized hydrothermally from the self-assembly of lanthanide ions(Eu3+) with the flexible oxalic acid and the rigid pyridine-2,6-dicarboxylic acid ligands, respectively. It crystallizes in the triclinic system, space group P1 with a = 11.225(4), b = 12.390(5), c = 13.752(5)A, α = 89.228(7), β = 71.142(6), γ = 75.552(6)°, Dc = 2.317 g/cm^3, μ = 5.480 mm^-1, F(000) = 1150, Z = 2, the final R = 0.0351 and w R = 0.0949 for 8782 observed reflections with I 〉 2σ(I). Structural analysis reveals that complex 1 exhibits a three-dimensional metal-organic framework via π-π stacking interactions. In addition, complex 1 displays a red fluorescence emission in the solid state at room temperature, which corresponds to the 5D0 → 7F2 transition of Eu3+ ions.
基金Supported by Science and Technology Development Projects of Jilin Province(No.20150101007JC)
文摘In this work, we synthesized a new two-dimensional Cd(Ⅱ) coordination polymer, [Cd(1,4-NDC)(L)](1), by using mixed 1,4-naphthalenedicarboxylic acid(1,4-H2NDC) and typical chelating N-donor ligands 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline ligand(L). Compound 1 crystallizes in monoclinic, space group P21/n with a = 12.936(5), b = 15.245(5), c = 13.499(5) ?, β = 105.456(5)o, V = 2565.9(16) A^3, Z = 4, C(31)H(16)CdClFN4O4, Mr = 675.33, Dc = 1.748 g/cm^3, F(000) = 1344, μ(MoKa) = 1.011 mm^-1, R = 0.0350 and wR = 0.0926. In 1, each 1,4-NDC anion bridges three adjacent Cd(Ⅱ) atoms to give a two-dimensional layer structure. The L ligands are attached on both sides of the layer in chelating coordination modes. In addition, the N–H···O hydrogen bond between L and 1,4-NDC further stabilizes the layer structure of 1. Moreover, the solid state luminescent property of 1 was also investigated at room temperature.
基金Supported by the National Natural Science Foundation of China(Nos.51572050,21271050 and 21261004)the Guangxi Natural Science Foundation(Nos.2015GXNSFDA139007,2014GXNSFBA118055 and 2013GXNSFGA019008)
文摘A novel Cd(Ⅱ) coordination polymer with diacylhydrazide ligand N,N?-bis(3-methoxysalicyl)-2,6-pyridinedicarbohydrazide(H_6msphz),[Cd_2(H_2msphz)(Py)_4]_n(1,Py = pyridine) has been synthesized through solvothermal reaction and structurally characterized by single-crystal X-ray diffraction,IR,TGA and PXRD investigations. It crystallizes in triclinic system,space group P1,with a = 11.0230(11),b = 11.7264(15),c = 17.3395(14) ?,α = 70.520(9),β = 84.806(7),γ = 81.965(9)°,V = 2089.9(4) ?~3,Dc = 1.638 gcm^(–3),μ = 1.083 mm^(-1),F(000) = 1032,Z = 2 and S = 1.040. In complex 1,the H_2msphz4-ligand uses not only its coordinated pocket to catch one Cd(Ⅱ) ion,but also its two terminal groups to chelate other two Cd(Ⅱ) ions,leading to the formation of a chain structure. The adjacent chains are further assembled together by two kinds of π-π interactions between the Py rings,resulting in the finial double layered supramolecular structure. In addition,complex 1 is found to show photoluminescence in the solid state at room temperature,which can be ascribed to the intraligand π→π* transitions.
文摘A new Cd(II) coordination polymer with 2-nitroterephthalie acid (H2npa) and 1,4- bis(2-methyl-imidazol-l-yl) butane (bib) has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, IR and EA. Complex [Cd(npa)(bib)]n (1) is of orthorhombic system, space group Pcca with a = 16.1750(5), b = 9.8764(5), c = 15.5890(3) A, V = 2490.4(2) A3, Z = 4, Mr = 539.82, Dc = 1.440 g/cm3, F(000) = 1088,μ = 0.918 mm-1, the final R = 0.0320 and wR = 0.0775 for 2253 reflections with I 〉 2σ(I). X-ray diffraction analysis reveals that complex 1 displays a four-fold interpenetrated dia topology. Furthermore, the luminescent property for complex 1 is also investigated in solid state at room temperature.
基金supported by the National Natural Science Foundation of China(No.21401121)Natural Science Foundation of Shaanxi Province(No.2014JQ2061)Doctor Foundation of Shaanxi Unversity of Science&Technology(BJ14-22)
文摘Three new supramolecular polymers, [(IP)(H2SO4)(H2O)](1), [(H2SDC)(BPA)](2) and [Mn(SDC)(IP)2]n (3), have been constructed by three modes(rigid IP, rigid SDC + flexible BPA, rigid IP + rigid SDC). Polymers 1 and 2 are supramolecular structures, assembled by hydrogen bonds and π···π interactions. X-ray structure analysis of 3 shows waved 1D chains which form a 3D supramolecular network by hydrogen bonds and π···π interactions. Solid-state properties of thermal stability, luminescent properties, and X-ray powder diffractions for these crystalline materials have also been investigated, and polymer 3 is considered to be a good stable luminescence material.
基金supported by the National Natural Science Foundation of China(Nos.21173164 and 21473133)
文摘Two new Zn~Ⅱ coordination polymers,namely,[Zn L(o-bdc)]n(1) and [Zn L(mbdc)]_n·n H_2O(2)(L = 4?-(3-pyridyl)-3,2?:6?,3??-terpyridine,H_2(o-bdc) = benzene-1,2-dicarboxylic acid,H_2(m-bdc) = benzene-1,3-dicarboxylic acid),were synthesized by hydrothermal methods. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic C2/c space group,with a = 28.016(2),b = 11.3815(11),c = 19.8071(17) ?,β = 133.961(2)°,V = 4546.2(7) ?3,Z = 8,Mr = 539.83,Dc = 1.577 Mg/m^3,μ = 1.127 mm-1,F(000) = 2208,the final R = 0.0426 and w R = 0.0986 for 2875 observed reflections with I 〉 2σ(I) and displays a 1D coordination chain. While compound 2 crystallizes in monoclinic C2/c space group,with a = 15.6003(14),b = 11.9152(11),c = 26.633(3) ?,β = 94.320(2)°,V = 4936.5(8) ?~3,Z = 4,M_r = 1115.67,Dc = 1.496 Mg/m^3,μ = 1.043 mm^(-1),F(000) = 2272,the final R = 0.0499 and w R = 0.1342 for 2659 observed reflections with I 〉 2σ(I) and shows a classical 3D cds topological network with point symbol of {65.8}. Furthermore,thermal stability and luminescent properties of 1 and 2 have also been investigated.
基金Supported by the Doctoral Scientific Research Foundation of Hengyang Normal University(16D06)Key Project of Industrial Science and Technology Support of Hengyang City(2015KG23)
文摘A new 1D copper(Ⅱ) polymer [Cu(Hpt)(3,5-DMBA)]n has been hydrothermally synthesized with copper acetate,3-(pyridin-2-yl)-1,2,4-triazole(Hpt) and 3,5-dimethylbenzoic acid(3,5-DMBA). It crystallizes in triclinic space group P1,with a = 8.1974(6),b = 8.3280(6),c = 12.5021(9) ?,α = 84.3320(10),β = 71.8870(10),γ= 65.4560(10)o,V = 737.44(9) ?~3,Dc = 1.612 g/cm3,Z = 2,F(000) = 366,GOOF = 1.035,R = 0.0298 and w R = 0.0855. The crystal structure is a one-dimensional(1-D) chain in which the Cu(Ⅱ) is five-coordinated with square pyramidal geometry. The crystal structure shows that the whole molecule consists of two copper ions bridged by two μ12-η:η0-3,5-dimethylbenzoic acid anions and two 3-(pyridin-2-yl)-1,2,4-triazole molecules. The coordination environment of Cu(Ⅱ) ion is CuO+2N_3. The luminescence and thermal properties of the complex were investigated.
基金financially supported by Foundation of Fujian Educational Committee(JA14348)
文摘A novel terbium(III) coordination polymer [Tb(C7H3NO4)(C6H4NO2)(H2O)] was successfully synthesized hydrothermally and characterized by single-crystal X-ray diffraction. The complex is of monoclinic, space group P21/c with a = 9.2252(11), b = 14.1477(16), c = 10.5134(12) A, β = 95.770(2)°, V = 1365.2(3) A3, Z = 4, Dc = 2.248 g·cm-3, F(000) = 880, the final R = 0.0176 and w R = 0.0411 for 2149 observed reflections with I 】 2σ(I). The complex is extended into a three-dimensional network structure with 24-atom rings which are composed of Tb, C and O atoms. The complex displays green fluorescence emission in the solid state at room temperature, which corresponds to 5D4 → 7F5 transition of the Tb(III) ion.
基金supported by the 973 Program of China(No. 2014CB845600)the NSFC(Nos.21421001 and 21290171)MOE Innovation Team(No.IRT13022) of China
文摘Two coordination polymers, {[Cu3(tci)2(DMAc)3].6DMAc-2H2O}n (1[) and {[Cu3(tci)2(tpt)2(H2O)2]- 2DMAc-2H2O}n (2) (H3tci = tris(2-carboxyethyl)isocyanurate, tpt = 2,4,6-tris(4-pyridyl)-l,3,5-triazine, DMAc = N,N-dimethylacetamide), have been constructed under solvothermal conditions. Both polymers were structurally characterized by single crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric (TG) analyses and powder X-ray diffraction (RXPD). 1 shows a (3,4)-connected 2D layer structure comprising Cu2(CO2)4 paddle-wheel units, which are further bridged by C-H.--O interactions to give a 3D supramolecular network. The introduction oftpt produces different framework for 2 that comprises a dinuclear and a mononuclear Cu(II) building units, which are further bridged together by tci3- and tpt ligands to give a 4-connected 2D topological net. Adjacent 2D layers are packed together via C-H...O interactions and π...π stacking interactions to form a 3D supramolecular structure. In addition, the luminescent properties and the solid-state UV-vis spectra of I and 2 were explored. Furthermore, antiferromagnetic exchange interactions were unveiled in the Cu2(COO)4 units of 1. ~ 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
基金Supported by the National Natural Science Foundation of China (No. 20771006)Education Committee of Anhui Province (KJ2008B005)
文摘A new 1-D coordination polymer [Cd(Hsal)2(bpp)2] 1 was hydrothermally synthesi- zed by self-assembly of the corresponding metal oxide and salicylic acid (H2sal) with exo-bidentate flexible dipyridyl ligand 1,3-bis(4-pyridyl)propane (bpp). X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic,space group C2/c with a = 18.942(3),b = 12.9309(19),c = 16.504(2) A,β = 120.072(2)°,V = 3498.3(9)A^3,Z = 4,C40H38CdN4O6,Mr = 783.14,Dc = 1.487 g/cm^3,μ = 0.679 mm^-1,F(000) = 1608,R = 0.0619 and wR = 0.1435 for 3153 observed reflections (I 〉 2σ(I)). The most remarkable feature of 1 lies in the 1-D chain by repeating [Cd2(bpp)2] units which consist of a 24-membered macrocyclic ring. The 1-D motifs are further connected by C–H… O hydrogen bonds to generate a 2-D structure. In addition,thermal stability and luminescent property of compound 1 were also documented.
文摘A new Pb(Ⅱ) coordination polymer, [Pb(1,4-chdc)(L)]_n·nH_2O(1), was synthesized under hydrothermal condition(1,4-H2 chdc = 1,4-cyclohexanedicarboxylic acid and L = 2-(3-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline). Its crystal structure was determined by singlecrystal X-ray diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 9.1182(8), b = 11.3249(10), c = 12.7326(12) A, α = 77.897(2), β = 81.644(2), γ = 84.491(2)°, V = 1269.0(2) A^3, Z = 2, C_(27)H_(24)FN_4O_5Pb, M_r = 710.69, D_c = 1.860 g/cm^3, F(000) = 690, μ(MoKa) = 6.701 mm^(-1), R = 0.0349 and wR = 0.0746. In 1, each 1,4-chdc anion bridges two neighboring Pb(Ⅱ) atoms in a bidentate chelating coordination mode to give a chain structure. The L ligands are attached on one side of the chain through chelating the Pb(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. The O-H···O and N-H···O hydrogen bonding interactions further stabilize the supramolecular layer structure of 1. Moreover, solid state luminescent property of 1 was also studied.
基金supported by the Science and Technology Development Project of Jilin Provincial Science&Technology Department(201205080)the Science and Technology Research Projects of the Education Office of Jilin Province(No.2013.384)
文摘A new complex [Zn(4-nph)(bib)](2n)·nH2O(1) has been obtained by the reaction of metal(Zn(Ⅱ)),1,4-bis(imidazol-1-yl)-butane(bib) with 4-nitrophthalic acid(4-H(2nph)).The crystal structure of 1 has been determined by single-crystal X-ray diffraction analysis.Compound 1 is of triclinic system,space group P1 with a = 10.3251,b = 12.4503,c = 16.6497 A,α = 88.487(3),β = 72.529(3),γ = 79.991(3)°,V = 2009.8(5)A^3 and Mr = 945.47.Complex 1 shows a three-dimensional(3 D) framework.Moreover,through intermolecular hydrogen bonds,compound 1 is assembled into a supramolecular structure.The thermal stability and luminescent properties of 1 are also investigated.
基金supported by the National Natural Science Foundation of China(No.51477002,21301005)Natural Science Foundation of Anhui Province(1408085QB31)
文摘One new chiral metal-organic coordination polymer,[Cd2(dpb)(H2hfipbb)2]n,was obtained under hydrothermal conditions of 1,3-di(pyridineyl)benzene(dpb) and 4,4'-(hexafluoroisopropylidene)bis(benzoic acid)(H2hfipbb). The title compound reveals a three-dimensional(3D) framework with two types of helical chains [Cd(COO)]n,which are linked each other to further form a double helical chain [Cd2(COO)2]n by sharing the same Cd(Ⅱ) ions. The dpb connects the double helical chains to generate a 3D framework. These unique structures were studied by single-crystal X-ray and other spectroscopy techniques. In addition,the luminescent,fluorescence lifetime and second harmonic generation efficiency properties in the solid state have been studied.
基金supported by the Natural Science Foundation of Yan’an University(YD2014-06)the Natural Scientific Research Foundation of Yan’an City Technology Division(2014ZC-3)the Provincial College Students’Innovation and Entrepreneurship Training Program(1452)
文摘A new Cd(Ⅱ) coordination polymer,{[Cd(pda)(bimb)]·(H2O)(0.5)}n(1,H2pda=1,3-phenylenediacetic acid,bimb = 4,4-bis(1-imidazolyl)biphenyl),has been synthesized and characterized by elemental analysis,IR spectroscopy,powder X-ray diffraction(PXRD) analyses and single-crystal X-ray diffraction techniques. Complex 1 shows a 4-connected two-fold interpenetrated three-dimensional(3-D) cds topology. In additional,photoluminescent properties of 1 and its dehydrated product have also been studied.
基金Supported by the Science and Technology Research Projects of the Education Committee of Jilin Province(No.2013206)
文摘A new 1D Cd(II) coordination polymer, [Cd(H2biim)2(SO4)]n·3n H2O(1, H2 biim = 2,2’-H2biimidazole), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 6.8405(14), b = 17.792(4), c = 14.987(3) A, β = 92.68(3), V = 1822.1(6) A3, Z = 4, C12H18 Cd N8O7S, Mr = 530.80, Dc = 1.935 g/cm3, F(000) = 1064, μ(Mo Ka) = 1.371 mm-1, R = 0.0280 and w R = 0.0617. In 1, adjacent Cd(II) atoms are bridged by sulfate anions in bidentate modes to yield a 1D chain. H2 biim ligands are located on both sides of the chain in chelating bidentate modes. Further, the H2 biim ligands from neighboring chains are paired through π-π interactions to generate a supramolecular layer, which is stabilized by the complicated N–H···O and O–H···O hydrogen bonds. In addition, thermal behavior and luminescent property of 1 have been investigated.
基金financially supported by the National Basic Research Program(No.2015CB931801)the National Natural Science Foundation of China(Nos.21204049 and 51473093)
文摘It is found that the fluorescence of aliphatic poly(amido amine)s including linear and hyperbranched ones can be dramatically enhanced by simple aggregation of polymer chains, attributing to the formation of a variety of intra- and interchain clusters with shared lone-pair electrons and the restriction of intramolecular motions. Thanks to the combination of strong solid fluorescence and excellent biocompatibility, these non-conjugated polymers become promising candidates for bioimaging such as bacterial detection. This finding not only extends the aggregation-induced emission(AIE) systems from conjugated compounds to non-conjugated materials, which expands the bioapplication range of AIE systems, but also sheds light on the exploration of novel unconventional luminogens.
基金financially supported by the National Natural Science Foundation of China (Nos. 51773009, 51573012 and 51373013)
文摘A novel photonic composite film based on a luminescent dicyanodistyrylbenzene-based liquid crystal polymer network(LCN) was fabricated by using a silica colloidal crystal as a template. The upper part of inverse opal structure and the luminescence characteristics of dicyanodistyrylbenzene-based moiety endowed the resulting bilayer photonic film with structural color arising from coherent Bragg reflection and fluorescence properties, respectively. A fluorescence enhancement phenomenon was observed in the photonic film due to the overlap between the reflection band and emission band of the fluorescent LCN. More importantly, the photo-induced irreversible Z/E photoisomerization of dicyanodistyrylbenzene-based moiety in the photonic film led to both a reflection spectral shift and an observable fluorescence variation. On the basis of this effective phototuning process, microscopic patterning of photonic film was developed under both fluorescence mode and reflection mode. The work demonstrated here provides a new route to construct photo-responsive photonic film.
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.21875143,21674065,and 21975215)the Innovation Research Foundation of Shenzhen(Nos.SGG20190222175202275,JCYJ20180507182229597,and JCYJ20180305125649693)the Natural Science Foundation of Guangdong Province(No.2016A030312002)。
文摘Why many luminescent liquid crystalline polymers(LLCPs)containing aggregation-induced emission luminogen(AIEgen)show weak emission is a question still to be answered.Herein,a series of LLCPs(α-Pns,n=4,8,and 12)with polynorbornene as main chain and twoα-dicyanodistyrylbenzene(α-DCS)as side chain are successfully synthesized to solve this issue.Differential scanning calorimetry(DSC),polarized light microscopy(PLM),one-dimentional(1D),two-dimentional(2D)middle-angle and wide-angle X-ray scattering(MAXS and WAXS)results demonstrate that the polymers form smectic A(SmA)phase with the side chains interdigitated packed within the smectic layers.Meanwhile,the photophysical properties ofα-Pns were investigated by ultraviolet-visible(UV-vis)absorption,steady state and time-resolved spectroscopy,and photothermal effect.Results show that the polymers are AIE active,but emit weak emission.The emission peak ofα-Pns film red-shift from 473 to 531 nm,the quantum yield gradually increases from around 1.6%to 14.7%,and the photothermal conversion efficiency decreases from 39%to 19%with the alkyl tail length increased.The photothermal effect,but not photoluminescence,dominates the excited state relaxation.