Synthesis and characterization of new coordination polymers generated from oxadiazole-containing organic ligands and inorganic silver(I) salts

The coordination chemistry of the oxadiazole-containing rigid bidentate ligands 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L2) and 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole (L3) with inorganic Ag(I) salts has been investigated. Four new coordination polymers were prepared by solution reactions and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. [[Ag(L2)]SO3CF3]n (1)(triclinic, P1; a = 10.1231(7) A, b = 13.9340-(10) A, c = 13.9284(10) A, alpha = 116.7300(10) degrees, beta = 94.6890(10) degrees, gamma = 108.7540(10) degrees, Z = 4) was obtained by the combination of L2 with AgOTf in a CH2Cl2/CH3OH mixed-solvent system and features a unique one-dimensional elliptical macrocycle-containing chain motif. The approximate dimensions of the rings are ca. 22 x 11 A. [[Ag-(L2)](ClO4)(CH3OH)0.5(H2O)0.5]n (2) (triclinic, P1; a = 8.4894(5) A, b = 13.9092(8) A, c = 14.1596(8) A, alpha = 71.1410(10) degrees, beta = 77.3350(10) degrees, gamma = 81.5370(10) degrees, Z = 4) was generated from the reaction of L2 with AgClO4 in a H2O/CH3OH mixed-solvent system and consists of one-dimensional chains that are linked to each other by weak noncovalent pi-pi interactions into two-dimensional sheets. Uncoordinated ClO4-counterions and guest solvent molecules are located between the layers. [[Ag(L2)]NO3]n (3) was obtained by the combination of L2 with Ag(NO3)2 in a MeOH/H2O mixed-solvent system (triclinic, P1; a = 8.3155(6) A, b = 8.8521(6) A, c = 9.8070(7) A, alpha = 74.8420(10) degrees, beta = 77.2800(10) degrees, gamma = 68.6760(10) degrees, Z = 2). In the solid state, it exhibits an interesting pair of chains associated with C-H...O hydrogen bonds. [[Ag(L3)]SO3CF3]n (4) is generated from L3 and AgSO3CF3 in a CH2Cl2/MeOH mixed-solvent system and crystallizes in the unusual space group Pnnm, with a = 7.9341(4) A, b = 11.5500(5) A, c = 18.1157(8) A, and Z = 4. It adopts a novel three-dimensional structural motif in the solid state with big rhombic channels (ca. 15 x 10 A).     

Synthesis and properties of disilanylene-containing polymers

Alternating polymers, poly[(disilanylene)ethynylene]s and poly[(1, 2-diethynylenedisilanylene)(1-silacyclopenta-2, 4-diene-3, 4-diyl)]s were prepared by the anionic ring-opening polymerization of 1, 2, 5, 6-tetrasilacycloocta-3, 7-diynes and 4, 5, 10-trisilacyclo[6.3.0]undeca-1(11), 8-diene-2, 6-diynes, respectively. Poly[(disilanylene)butenyne-1, 4-diyl]s were synthesized by the reaction of 1, 2-diethynyldisilanes with a catalytic amount of RhCl(PPh₃)₃. Photochemical and conducting properties of the polymers are described.     

Hydrodynamic and electrooptical properties of star-shaped heteroarm fullerene (C60)-containing polymers in solutions

Star-shaped heteroarm polymers with a C₆₀ branching center and polystyrene and poly(2-vinylpyridine) arms of equal molecular masses have been studied by the methods of molecular hydrodynamics (translational diffusion and viscometry) and electrooptics (the Kerr effect). The experimental hydrodynamic data are interpreted in terms of the regular star model. The molecular masses and hydrodynamic sizes of star-shaped heteroarm polymers in solutions are estimated. A comparison of these values with the corresponding parameters of linear polymer-analogs (polystyrene and poly(2-vinylpyridine)) makes it possible to characterize the branching degree of macromolecules. The study of the electrooptical properties of the heteroarm polymer in benzene demonstrates the tendency of macromolecules toward aggregation.     

Synthesis and photophysical properties of benzo[c]thiophene,p-phenylene-, triphenylamine-, and pyrene-based vinylenes

An efficient synthesis of benzo[c]thiophenyl/p-phenylenyl/pyrenyl phosphonate esters has been achieved using ZnBr₂-catalyzed Michaelis–Arbuzov reaction of corresponding benzyl alcohol/bromides at room temperature. Horner–Wadsworth–Emmons reaction of the phosphonate esters with aryl/heteroaryl aldehydes in the presence of t-BuOK furnished the vinylenes in good yields. The absorption and emission characteristics of the synthesized vinylenes were also reported.     

Synthesis and properties of tetrazole-containing double polymers

Based on poly(5-vinyltetrazole) and a copolymer of 2-methyl-5-vinyltetrazole with 2-(vinyloxyethoxy)methyloxirane, tetrazole-containing network double polymers capable of gelation both in organic media and in water have been obtained. It has been shown that the covalent bonding of linear polymer macromolecules is the result of alkylation of unsubstituted N-H tetrazole cycles of poly(5-vinyltetrazole) with oxirane cycles incorporated into the copolymer structure.     

Synthesis and optical properties of metallo-supramolecular polymers

Metal-ligand interactions between metal ions, such as Zn2+, and ditopic low-molecular weight conjugated monomers, which utilize the 2,6-bis(1'-methylbenzimidazolyl)pyridine ligand, lead to the formation of supramolecular conjugated polymers with interesting optical properties.     

Synthesis and properties of cyclopropane-containing optically transparent polymers

New cyclopropane-containing optically transparent polymers were prepared by radical homopolymerization of p-(2-methoxycarbonylcyclopropyl)styrene and by its binary copolymerization with styrene and methyl methacrylate. The composition and structure of these macromolecular compounds were determined, and their main service characteristics were evaluated.     

Synthesis and electrical properties of substituted paracyclophane polymers

We report the synthesis of three new substituted [6.2]paracyclophane-1,5-dienes and their conversion to medium molecular weight polymers by an intra/intermolecular cyclopolymerization. These materials can be oxidatively “doped” by exposure to iodine vapor to give semiconductor properties.     

Synthesis, characterization and thermal properties of metaloquinolate-containing polymers

The monomer, 5-methyl(2-methacryloylethyloxy)-8-quinolinol(HEMA-CH₂-Hq), which possesses both double bond and 8-hydroxyquinoline groups, was synthesized from 2-hydroxyethyl methacrylate (HEMA) and 5-chloromethyl-8-quinolinol hydrochloride. The model polymer with 8-hydroxyquinoline ligands was obtained by free-radical copolymerization with styrene. So metaloquinolate (AlQ₃, ZnQ₂)-containing polymers are prepared by coordinating reaction with di(8-hydroxyquinoline) aluminum(AlQ₂) chelates or mono(8-hydroxyquinoline) zinc(ZnQ) chelates without cross-linking. Both polymer and polymer complexes were analyzed by FT-IR, UV-vis, DSC, TGA and photoluminescence spectroscopies. They are soluble in common solvents and easy to form films. The use of AlQ₂ and ZnQ avoided the cross-linking caused by the AlQ₃, ZnQ₂ formation between different polymer chains. High glass transition temperature, good thermal stability, and strong yellow-green fluorescence were observed for the prepared polymers. These polymers were expected to have the potential application in yellow-green OLEDs.     

Synthesis and properties of carbazole‐layered polymers

New aromatic ring‐layered polymers consisting of carbazole as a layered aromatic group and xanthene as a scaffold were designed and synthesized via the Sonogashira–Hagihara coupling reaction. Their optical and electrochemical behaviors were investigated in detail; the results showed that these polymers could be used as hole‐transporting materials. Polymers with nitrobenzene moieties at the polymer chain ends quenched the emission from the layered carbazoles to the nitrobenzene termini; thus, the polymers acted as the molecular wire that transferred photoexcited energy and/or electrons to the polymer termini. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4279–4288, 2009     

Synthesis and optoelectronic properties of amino-functionalized carbazole-based conjugated polymers

A series of alcohol soluble amino-functionalized carbazole-based copolymers were synthesized via Suzuki coupling reaction.The pendent amino groups endow them high solubility in polar solvents,as well as efficient electron injection capability from high work-function metals.The relationships between the photophysical and electrochemical properties and the polymer backbone structure were systematically investigated.These alcohol-soluble carbazole-based copolymers were used as cathode interlayers between the high work-function metal Al cathode and P-PPV emissive layer in polymer light-emitting diodes with device structure of ITO/PEDOT:PSS/P-PPV/interlayer/Al.The resulting devices exhibited improved performance due to the better electron injection/transporting ability of the designed copolymers from Al cathode to the light-emitting layer.     

Synthesis of rare-earth metal-containing polymers and their fluorescence properties

Four kinds of polymeric β-diketone compounds, including poly(vinylbenzyldibenzoylmethane)(1), poly(vinylbenzylacetoacetone)(2), poly(vinylbenzyl-2-thenoyltrifluoroacetone)(3) and poly(p-benzoylacetylstyrene)(4) were synthesized. And then polymeric β-diketone-europium(III), -terbium(III), -samarium(III), -dysprosium(III), -europium(III)-gadolinium(III), -terbium(III)-gadolinium(III), and -europium(III)-terbium(III) chelates were also synthesized. The chelate structures were confirmed. The influence of the structure on the fluorescence properties was investigated. The fluorescence intensity of polymeric rare-earth metal complexes is closely related to the ligand and metal content. Polymeric complexes possess a higher fluorescence stability than that of corresponding low-molecular-weight complexes.     

Synthesis and photochromic properties of polymers containing spirooxazine groups

Two spirooxazine (SO) compounds containing bromobutyl substituents on 1-position (SO1) and 9′- position (SO2) have been synthesized and characterized by 1H-NMR, IR and ESI-MS in this paper. SO1-g-PMMA and SO2-g-PMMA polymer were prepared by grafting SO1 and SO2 onto PMMA through C-Br bonding sites. Also, SOs were doped into PMMA matrix to afford SO1-d-PMMA and SO2-d-PMMA. Photochromic behaviors of these compounds have been studied. Compared with SO1, SO2 exhibited better photoresponse and slower bleaching in dichloromethane solution. Inserted into polymer films, the decoloration process of SOs were significantly retarded and it was found that the fading curves fitted a first-order equation; As regard to four polymers, 1-position grafting (SO2-g-PMMA) can cause a higher reduction degree on the thermal fading rate.     

Quantum-chemical calculation of electrooptical properties of vanillin tautomers

Static dipole polarizabilities and hyperpolarizabilities of benzoid and p-quinoid molecular forms of vanillin were calculated using quantum-chemical method B3LYP/cc-pVTZ. The dominant benzoid tautomers much exceed in hyperpolarizability the m-nitroaniline molecule. Tautomeric transformations and conformational changes significantly affect the vanillin hyperpolarizability. Quinoid tautomers generated by the topochemical reaction of proton transfer between neighboring molecules in a vanillin crystal can promote the second harmonic generation of infrared laser light only as an element of supramolecular nanostructures (linear defects) with a high hyperpolarizability.     

金属卟啉分子印迹聚合物的合成与性能研究

以5-(4-羟基苯基)-10,15,20-三苯基卟啉锌为印迹分子,4-乙烯基吡啶为功能单体,乙二醇二甲基丙烯酸酯为交联剂,合成了具有金属卟啉识别能力的分子印迹聚合物.紫外可见滴定光谱研究表明,功能单体与印迹分子在聚合前形成1:1的配合物.通过吸附试验、荧光光谱及斯卡查特分析法,考察了分子印迹聚合物对锌卟啉化合物的识别性能.结果表明,印迹聚合物对结构类似的卟啉化合物具有良好的识别能力,对印迹分子荧光性能的影响远大于其对应的非印迹聚合物.在浓度较低时,印迹聚合物对印迹分子的结合常数和最大结合量分别为:1.61×106L/mol和3.22×10-5mol/g.     

Synthesis and optical properties of some novel arylene-alkynylene polymers

The synthesis and the optical properties of the novel aryleneethynylenes ( 7 , 8 ) and arylenebutadiynylenes ( 10 , 11 ) using either a Heck-type or a Hay-type coupling are reported. The route reported here also makes meta-linked arylene-alkynylenes accessible. The number-average degree of polymerization of the obtained polymers is between 13 and 60. Some of the materials show promising optical properties (photoluminescence).     

胺基功能化咔唑共轭聚合物的合成及其光电性能研究

发展了新型含有胺基的支化烷基修饰的咔唑单元,并且与芴、咔唑、苯等单元通过Suzuki偶联反应共聚得到不同主链结构的水/醇溶共轭聚合物界面修饰材料,研究了主链结构的变化对材料光物理、电化学性能的影响.所有聚合物均被用作阴极界面材料应用于器件结构为ITO/PEDOT：PSS/P-PPV/界面层/Al的聚合物发光二极管中.在相同器件制备条件下,系统比较了不同主链结构的界面修饰材料在器件中的性能,并研究了性能差异的原因.器件研究结果表明,在高功函数金属Al阴极的聚合物发光二极管中,含胺基功能化咔唑单元的水/醇溶共轭聚合物材料由于界面偶极的形成,均表现出很好的电子注入/传输性能,与之对应的器件性能得到大幅提升.     

Synthesis and optoelectronic properties of novel benzodifuran semiconducting polymers

Two new semiconducting polymers poly{4,8‐bis(4‐decylphenylethynyl)benzo[1,2‐b:4,5‐b′]difuran} ( P1 ) and poly {4,8‐bis(4‐decylphenylethynyl)benzo[1,2‐b:4,5‐b′]difuran‐alt‐4,8‐bis(4‐decylphenylethynyl)benzo[1,2‐b:4,5‐b′]dithiophene} ( P2 ) have been synthesized. These polymers were tested in bulk heterojunction solar cells yielding power conversion efficiencies of 1.19% for P1 and 0.79% for P2 . The surface morphology of the solar cell devices indicated that both the polymers display a granular morphology with smoother films displaying higher power conversion efficiencies. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and opto-electronic properties of functionalized pyrimidine-based conjugated polymers

Side chain engineering has been used for tuning the opto-electronic properties of organic semiconductors. In this work, a series of pyrimidine-based donor-acceptor (D-A) conjugated polymers functionalized with electron-withdrawing or electron-donating side chains were synthesized. The opto-electronic properties of the pyrimidine D-A conjugated polymers were investigated focusing on the dependence on the electron withdrawing strength of the acceptor moiety, while maintaining the same donor moiety. Fine-tuning of the energy levels was achieved by introducing electron donating (alkoxy [ OR] and alkylthio [ SR]) or electron withdrawing (alkylsulfinyl [ SOR] and alkylsulfonyl [ SO₂R]) side chains onto the acceptor moiety. The effects of side chain modification have been investigated through DFT calculations, UV–vis analysis, and electrochemical measurements. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2547–2553