Syntheses,Crystal Structures and Luminescent Properties of Two Lanthanide Coordination Polymers Based on Bifunctional Ligand

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.

A Chain Cadmium(Ⅱ) Coordination Polymer with Diacylhydrazide: Synthesis,Crystal Structure and Luminescent Property

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.

Hydrothermal Synthesis, Crystal Structure and Luminescent Property of a New Cd(Ⅱ) Coordination Polymer with Four-fold Interpenetrated dia Topology

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.

Syntheses,Structures and Photoluminescent Properties of Cd(Ⅱ)Polymeric Complexes Based on 5-Aminoisophthalic Acid and Bipyridine Co-ligands

Two novel complexes, namely {[Cd（AIP）（4,4＇-bpy）]·1.3DMF}n（1） and [Cd（AIP）（2,2＇- bpy）]n（2）, have been synthesized through solvothermal reaction（H2AIP = 5-aminoisophthalic acid, 2,2＇-bpy = 2,2＇-bipyridine, 4,4＇-bpy = 4,4＇-bipyridine, and DMF = N,N＇-dimethylformamide） and structurally determined by single-crystal X-ray diffraction. Complex 1 shows a three-dimensional（3D） layer-pillar framework with rectangular channels, while complex 2 displays a two-dimensional（2D） wave net architecture. Furthermore, 1 and 2 were characterized by elemental analysis, infrared spectra（IR）, thermal gravimetric analyses（TGA） and fluorescence measurements. The luminescent properties of 1 dispersed in various organic solvents have been investigated systematically, demonstrating high selectivity for acetone via the fluorescence quenching effect.

Hydrothermal Synthesis,Crystal Structure and Properties of a 1D Chain Copper(Ⅱ) Polymer with 3-(2-Pyridiyl)-1H-1,2,4-triazole(Hpt)

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.

Synthesis and Crystal Structure of a New Zinc(Ⅱ)Coordination Polymer Assembled by 4-Nitrophthalic Acid and Bis(imidazol)Ligands

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.

Syntheses,Structures,and Properties of Three New Polymers Based on Flexible and Rigid Ligands

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.

Structure and Photochemical Properties of a Chiral Cd Coordination Polymer Based on 4,4'-(Hexafluoroisopropylidene)Bis(benzoic acid)and 1,3-Di(pyridineyl)benzene

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.

A Cd(Ⅱ)Coordination Polymer with cds Topology Constructed by Polycarboxylate and Imidazole-containing Ligand

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.

Syntheses,Structures and Properties for Zn~Ⅱ Coordination Polymers Based on a Functional 4'-(3-Pyridyl)-3,2':6',3''-terpyridine Ligand

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.

A Luminescent Dicyanodistyrylbenzene-based Liquid Crystal Polymer Network for Photochemically Patterned Photonic Composite Film

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.

Syntheses,structures,luminescent and magnetic properties of two coordination polymers based on a flexible multidentate carboxylate ligand

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.

Through-space charge transfer polymers for solution-processed organic light-emitting diodes

Through-space charge transfer(TSCT)polymers are an attractive class of luminescent polymers with spatial donor/acceptor architecture and thermally activated delayed fluorescence effect,different from conventional luminescent polymers with conjugated donor-acceptor structure and through-bond charge transfer emission.Their emission comes from the intramolecular charge transfer by through-space pathway because the donor and acceptor segments are spatially proximate to each other in each repeating unit but are physically separated by nonconjugated polymer backbone.In this review,recent advances in TSCT polymers with linear,bottlebrush,and dendritic architectures are presented,with the focus on their molecular design,photophysical behavior,and device performance.We hope that this review shall provide a useful insight of new luminescent polymers with TSCT effect for use in solution-processed organic light-emitting diodes.

Aggregation-induced Emission of Non-conjugated Poly(amido amine)s:Discovering,Luminescent Mechanism Understanding and Bioapplication

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.

Lithium ion conduction and ion-polymer interaction in poly(vinyl pyrrolidone) based electrolytes blended with different plasticizers

Poly（ethylene oxide）, poly（vinyl pyrrolidone）（PEO/PVP）, lithium perchlorate salt（Li Cl O4） and different plasticizer based, gel polymer electrolytes were prepared by the solvent casting technique. XRD results show that the crystallinity decreases with the addition of different plasticizers. Consequently, there is an enhancement in the amorphousity of the samples responsible for the process of ion transport. FTIR spectroscopy is used to characterize the structure of the polymer and confirms the complexation of plasticizer with host polymer matrix. The ionic conductivity has been calculated using the bulk impedance obtained through impedance spectroscopy. Among the various plasticizers, the ethylene carbonate（EC） based complex exhibits a maximum ionic conductivity value of the order of2.7279 10 4S cm 1. Thermal stability of the prepared electrolyte films shows that they can be used in batteries at elevated temperatures. PEO（72%）/PVP（8%）/Li Cl O4（8%）/EC（12%） has the maximum ionic conductivity value which is supported by the lowest optical band gap and lowest intensity in photoluminescence spectroscopy near 400–450 nm. Two and three dimensional topographic images of the sample having a maximum ionic conductivity show the presence of micropores.

AIEgen containing side-chain liquid crystalline polymers: Photoluminecence or photothermal, which dominate?

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.

Emission properties and energy transfer in Perylene-Rhodamine 6 G co-doped polymeric fiber

This Letter presents the fabrication and characterization of a perylene（Per） and Rhodamine 6 G（Rh 6 G）co-doped polymeric fiber. The spectroscopic properties（luminescence spectra, attenuation, energy transfer）of the co-doped polymethyl methacrylate（PMMA） fiber are presented. Two different concentrations of Rh 6 G（2.2 × 10^（-4） and 4.1 × 10^（-4）mol∕L） and a constant Per concentration（6.2 × 10^（-4）mol∕L） are used in the experiments. The luminescence spectrum changes versus the fiber length are discussed. Additionally, the ratio of the maximum fluorescence peaks of the used dyes is calculated versus the fiber length. The obtained results show the energy transfer from Per（donor） to Rh 6 G（acceptor）. The proposed co-doped fiber can be used in applications in lighting and sensor technology.

Luminescent properties of Tb^(3+)-doped poly(methyl methacrylate) fiber

Lanthanide-doped polymers are very attractive, since they can be used for luminescent optical fiber fabrications.This Letter presents the terbium-ions-doped poly（methyl methacrylate） fiber fabrication and spectroscopic characterization. The measured excited state（5D4） lifetime of 0.741 ms confirms that a used organometallic can be used to obtain an intense luminescence in a polymeric fiber. The luminescence spectrum shape modification versus the fiber length is also investigated.

Nonconventional aggregation-induced emission polysiloxanes:Structures,characteristics,and applications

Nonconventional luminescent materials have been rising stars in organic luminophores due to their intrinsic characteristics,including water-solubility,biocompatibility,and environmental friendliness and have shown potential applications in diverse fields.As an indispensable branch of nonconventional luminescent materials,polysiloxanes,which consist of electron-rich auxochromic groups,have exhibited outstanding photophysical properties due to the unique silicon atoms.The flexible Si-O bonds benefit the aggregation,and the empty 3d orbitals of Si atoms can generate coordination bonds including N→Si and O→Si,altering the electron delocalization of the material and improving the luminescent purity.Herein,we review the recent progress in luminescent polysiloxanes with different topologies and discuss the challenges and perspectives.With an emphasis on the driving force for the aggregation and the mechanism of tuned emissions,the role of Si atoms played in the nonconventional luminophores is highlighted.This review may provide new insights into the design of nonconventional luminescent materials and expand their further applications in sensing,biomedicine,lighting devices,etc.