PREPARATION AND CHARACTERIZATION OF SCHIFF BASE POLYMERS DERIVED FROM 4,4''''-METHYLENEBIS(CINNAMALDEHYDE)

New Schiff base polymers poly[4,4'-methylenebis(cinnamaldehyde)ethylenediimine] (PMBCen), poly[4,4'-methylenebis(cinnamaldehyde) 1,2-propylenediimine] (PMBCPn), poly[4,4'-methylenebis(cinnamaldehyde) 1,3-propylenediimine] (PMBCPR), poly[4,4'-methylenebis(cinnamaldehyde)l,2-phenylenediimine] (PMBCPh), poly[4,4'-methylene-bis(cinnamaldehyde)meso-stilbenediimine] (PMBCS), poly[4,4'-methylenebis(cinnamaldehyde)urea] (PMBCUR), poly[4,4'-methylenebis(cinnamaldehyde)semicarbazone] (PMBCSc), poly[4,4'-methylenebis(cinnamaldehyde)thiosemicarbazone] (PMBCTSc) and poly[4,4'-methylenebis(cinnamaldehyde)hydrazone] (PMBCH) were formed by polycondensation of 4,4'-methylenebis(cinnamaldehyde) with ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2-phenylenediamine, meso-stilbenediamine, urea, semicarbazide, thiosemicarbazide and hydrazine, respectively. The dialdehyde and polymers have been characterized through elemental micro-analysis, IR, UV-Vis and 'H-NMR spectroscopic techniques. Thermoanalytical studies and viscous flow of dilute solutions of dialdehyde and its polymers have been examined and compared.     

Syntheses and Crystal Structures of Two Coordination Polymers of Cobalt and Cadmium Assembled by 4,4ˊ-(Ethane-1,2-diyldioxy)dibenzoic Acid

Two new metal-organic coordination polymers [Co0.5（Heoba）（bib）0.5]2n（1） and [Cd（eoba）（phen）]n（2）（H2eoba = 4,4-（ethane-1,2-diyldioxy）dibenzoic acid, bib = 1,4-bis（imidazol-1-yl）-butane, phen = 1,10-phenanthroline） have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. Complex 1 is a 2D network structure, and complex 2 exhibits a 3D network structure. Moreover, the luminescent property of complex 2 has been investigated in the solid state.     

Novel Donor-Acceptor Copolymers Based on Dithienosilole and Ketone Modified Thieno[3,4-b]thiophene for Photovoltaic Application

Two novel donor-acceptor （D-A） copolymers containing dithienosilole （DTS） donor unit and ketone modified thieno[3,4-b]thiophene （TT） acceptor unit, namely, poly{4,4＇-bis（2-ethylhexyl）dithieno[3,2-b：2＇,Y-d]silole-5,5＇-diyl- alt-l-（thieno[3,4-b]thiophen-2-yl）-2-ethylhexan-l-one} （PDTSTT） and poly{4,4＇-bis（2-ethylhexyl）dithieno[3,2- b：2＇,3＇-d]silole-5,5＇-diyl-alt- 1-（4,6-bis（4-ethylhexylthien-2-yl）thieno[3,4-b]thiophen-2-yl）-2-ethylhexan- 1-one} （PD- TSDTTT）, were synthesized for the application in polymer solar cells （PSCs）, and the effects of thiophene bridge on the structural geometry and photovoiltaie performance have been investigated. The polymer PDTSTT and PDTSDTTT have the electrochemical bandgaps of 1.54 and 2.02 eV, together with low-lying HOMO energy levels of-5.47 and -5.37 eV, respectively. Molecular geometry simulation result shows that compared with PDTSTT, the insertion of thiophene bridge in PDTSDTTT can well relieve the steric hindrance between the TT and DTS unit, as confirmed by the reduced dihedral angle between DTS and DTTT unit. Under the illumination of AM 1.5G, 100 mW/cm2, the PSC based on PDTSDTTT/PC61BM （1 ： 1, w ： w） demonstrates a power conversion efficiency of 1.0%, which is significantly improved in comparison with the device based on PDTSTT/PC61BM （1 ： 2, w ： w） under the same experimental condition. This is because the enhanced planarity and increased effective conjugation of the main chain in PDTSDTTT promote the more favorable morphology for charge transportation, although PDTSTT possesses the broader absorption band than PDTSDTTT.     

Preparation and Nonlinear Optical Property of Azobenzene Substituted Polyacetylene

Two new functional polyacetylenes bearing different azobenzene group, -{ HC=C[azo-N （CH3）CH2CH2OH] } n-, [poly（EHAB）; azo = 4,4＇-azobenzene] and - { HC=C[azo-N（CH3）CH2CH2O COC3H7]},-, [poly（EEAB）]} were prepared by [Rh（nbd）Cl]2-Et3N catalysts. Poly（EHAB） has poor solubility while poly（EEAB） can be dissolved in common solvent. The polymers were characterized by FHR, ^1H NMR, UV and GPC. The nonlinear optical property of the soluble poly（EEAB） was investigated with 8 ns width pulse at 532 nm by Z-scan technique. The results show that poly（EEAB） is endowed with the larger third-order nonlinear optical property.     

Syntheses,Electrochemical Behaviors,Spectral Properties and DFT Calculations of Two 1,3-Dithiole Derivatives

Two new 1,3-dithiole derivatives, 4,4＇-{9-[4,5-bis（methylthio）-1,3-dithiol-2-ylidene]-9H-fluorene-2,7- diyl} dipyridine（2a） and 3,3＇-{9-[4,5-bis（methylthio）-1,3-dithiol-2-ylidene]-9H-fluorene-2,7-diyl} dipyridine（2b） were synthesized and characterized by Fourier transform infrared（FTIR）, 1H NMR, 13C NMR and mass spectroscopies. The crystal structure of compound 2b was also studied. The optimized conformations and molecular orbital diagrams of compounds 2a and 2b were illustrated via density functional theory（DFT）. By the time-dependent DFT（TD-DFT） method, electronic absorption spectra of compounds 2a and 2b were predicted and the results achieved were in good agreement with the experimental data. The formation of the cationic radical during the electrochemical oxidation process was also proposed.     

A Convenient Synthesis of 2-Arylnaphtho[1,2-d]oxazole Derivatives Promoted by Triethylamine

A variety of 2-arylnaphtho[ 1,2-d]oxazole derivatives were efficiently synthesized in moderate to high yields by the reaction of aromatic aldehydes with 1-amino-2-naphthol derivatives in the presence of triethylamine in refluxing ethanol in air. Seven new 2-arylnaphtho[1,2-d]oxazole derivatives were obtained and characterized by the spectral data and elemental analysis. In addition, the X-ray crystal structures of 2-[4-（N,N-dimethylamino）phenyl]naphtho[ 1,2-d] oxzole （3d） and 1, 1＇-bis（naphtho[ 1,2-d]oxazol-2-yl）ferrocene （3n） have been determined.     

STUDIES ON BIPYRIDINIUM SALTS AND THEIR POLYMERS Ⅰ. SYNTHESIS OF 4, 4''-(1, 4-PHENYLENE-)BIS-[N-ALKYL (ARYL)-2, 6-DIPHENYL-] PYRIDINIUM SALTS AND THEIR POLYMERS FROM CORRESPONDING BIPYRYLIUM SALT*

The reaction of pyrylium salt with primary amine has been utilized to synthesize 4,4'-bipyri-dinium salts and pyridinium polymers. Seven new 4,4'-(1,4-phenylene-) bis-[N-alkyl(aryl)-2,6-diphenyl-] pyridinium perchlorates 4 and five corresponding bipyridinium polymers 5 were preparedwith good yields from 4,4'-(1,4-phenylene-) bis-(2,6-diphenyl-) pyrylium perchlorate 3. Preliminarytests have been made for their redox behavior and catalytic activity.     

The Electroluminescence Characterization of Poly(p-phenyleneethynylene)——The π-conjugated Backbone Interrupted by a Butylene Unit

IntroductionSince the firstreport in1 990 of the electro- lu-minescence of the conjugated polymers in the filmof poly(p- phenylenevinylene) sandwiched betweenan anode and a cathode of appropriate work func-tions[1] ,enormous efforts have been devoted to thesynthesis of light emitting polymers[2— 4 ] .Owing toconjugated polymers′ photoluminescence and elec-troluminescence having been found out,their im-portant properties,polymer processability,bandgap tunability and mechanical flexibility mak…     

One-Pot Hydrothermal Synthesis of Two New Copper（Ⅱ） Complexes with 4-Carboxyphenoxy Acetic Acid

The one-pot hydrothermal reaction of CuCl2 with H2CPOA and 4,4＇-bpy results in two new coordination polymers, [Cu（CPOA）（4,4＇-bpy）（H2O）2]·1.5H2O （1） and [Cu2（HCPOA）4（4,4＇-bpy）4] （2） （H2CPOA=4-carboxyphenoxy acetic acid, 4,4＇-bpy=4,4＇-bipyridine） since CPOA^2- anions reach equilibrium with HCPOA^- anions in the reaction system. The crystal structure of 1 shows a triple interpenetration CdSO4-like net with 1D channel, in which lattice water molecules are located. Complex 2 is a ladder-like 1D double chain structure assembled through coordination bonds and O—H…N hydrogen bonds.     

Synthesis, Thermal, Electrical and Catalytic Studies of Some Transition Metal Polychelates of Bis-bidentate Schiff Base

Polychelates of Mn（Ⅱ）, Fe（Ⅱ）, Co（Ⅱ）, Ni（Ⅱ）, Cu（Ⅱ）, Zn（Ⅱ） and Cd（Ⅱ） with the bis salen-type ligand derived from 4,4＇-bis[（salicylaldehyde-5）azo]biphenyl and 1,4-diaminobutane have been synthesized. All the polychelalls have been characllrized by elemental analysis, magnetic susceptibility measurements, IR, electronic spectra and thennogravirncuic studies. All the complexes isolated in solid stall are dark coloured and insoluble in water and common organic solvents. The ligand behaves as a bis-bidentall molecule coordinating through the phenolic oxygen and azomethine nitrogen atoms. The thermal decomposition of these metal complexes was investigated by thermogravimetric analysis and data have been analyzed for kinetic parameters using Broido equation. The solid-state electrical conductivity of the ligand and its polychelalls in the form of compressed pellet was studied in the temperaturc range from 313 to 413 K All the polychelalls were found to show semiconducting nature. The Mn（Ⅱ）, Fe（Ⅱ）, Co（Ⅱ） and Ni（Ⅱ） polychelalls have been assessed for the catalytic epoxidation of styrene.     

Syntheses,Structures, and Properties of Three Coordiantion Polymers： [Cd2（bpp）1.5（Hbpp）（phen）2]n, [Mn3（Htptc）2（phen）2（H2O）2]n,and {[Cu（btc）0.5（1,4-bib）]？2H2O}nSyntheses,Structures, and Properties of Three Coordiantion Polymers： [Cd2（bpp）1.5（Hbpp）（phen）2]n, [Mn3（Htptc）2（phen）2（H2O）2]n,and {[Cu（btc）0.5（1,4-bib）]？2H2O}n

Hydrothermal reactions of three aromatic polycarboxylic acids and the transitional metal cations in the presence of phen and 1,4-bib afford three new coordination polymers： [Cd2（bpp）1.5（Hbpp）（phen）2]n （1）, [Mn3（Htptc）2（phen）2（H2O）2]n （2）, and {[Cu（btc）0.5（1,4- bib）]·2H2O}n（3） （H2bpp = 2,6-bis（4＇-carboxyphenyl）-4-phenylpyridine, H4tptc = terphenyl-2,5,2＇,5＇-tetracar- boxylic acid, H4btc =biphenyl-2,2＇,4,4＇-tetracarboxylic acid, phen =1,10-phenanthroline, and 1,4-bib = 1,4-bis（1H-imidazol-1-yl）benzene）. Their structures have been determined by single- crystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction （PXRD） analyses. In compound 1, the CdII cations are linked by bpp2- to form one ladder structure, based on which a 3D network is constructed with the help of non-covalent interactions. The topology of 2 is a 3D （3,4,5）-connected framework with the Point Schl？fli symbol of （42.6）2（43.62.8）（45.64.8）2. Compound 3 shows an unprecedented 3D （4,4）-connected framework with the Point Schl？fli symbol of （64.82）2（65.8）. Moreover, the luminescent property of 1 has been investigated.     

Syntheses and Crystal Structures of Two New Metal Phosphonates： [Mn（H2O）2（C12H8N2） （HO3PCH2CH2CO2） ] and [Co（H2O）4（C10H8N2）]-（HOaPCH2CH2CO2）

By the reactions of manganese（if） acetate, 2-sulfoethylphosphonic acid, 1,10-phen （1,10-phen = 1, 10-phenanthroline） or cobalt（Ⅱ） acetate, 4,4＇-bipy and 2-carboxyethylphosphonic acid, two novel compounds of [Mn（H2O）2（C12H8N2） （HO3PCH2CH2CO2） ] （1） and[Co（H2O）4（C10H8N2）]-（HOaPCH2CH2CO2） （2） have been synthesized and characterized by IR spectroscopy, elemental analyses and single-crystal X-ray diffraction. Compound 1 has a 0D structure. Two Mn（ii） ions are linked by two 2-carboxyethylphosphonic acid ligands, forming a centrosymmetric dimer. These dimers are further interlinked into a 2D layer structure by π-π stacking interactions and hydrogen bonds. Compound 2 has a 1D chain structure. The 2-carboxyethylphosphonic acid remains uncoordinated and acts as the organic template. By the bridge of 4,4＇-bipy, the [Co（4,4＇-bipy）]^2＋ chains are formed.     

Supramolecular Architecture from the Self-assembly of One-dimensionalCoordination Polymers and Hydrogen Bonds

The synthesis and characterization of coordination polymers have been a rapid growth area in recent years. The coordination polymers consist of 1D chains, 2D sheets or 3D networks in which metal-organic building blocks connected via coordinate and hydrogen bonds. They received considerable attention because of their versatile intriguing architectures, topologies and potential applications in materials1,2 . As rigid rod-like spacers, 4,4'-bipyridine and its analogues have been used to give r…     

Synthesis of Chiral Aminophenols Based on Proline and Their Application in Enantioselective Addition of Diethylzinc to Aldehydes

Three 2-{（3R, 7aS )-1, 1-disubstituted-tetrahydro-lH-pyrrolo [ 1,2- c ] [ 1,3 ] oxazol-3-yl} phenols have been synthesized from salicylaldehyde and amino alcohols derived from L-proline, and used as ligands in enantioselective addition of diethylzinc to aldehydes, the ee values of obtained secondary alcohols were found in the range of 0-90%.     

Interaction of benzene-1,3-disulfonylamid-kriptofix[22] with iodine in chloroform and dichloromethane solutions

The interaction of iodine as an cr-acceptor with a synthetic ligand,benzene-1,3-disulfonylamid-kriptofix[22]（BDSAK） as a π-donor has been investigated spectrophotometrically in chloroform（CHCl3） and dichloromethane（DCM） solutions.The results of mole ratio plots and Job＇s method show the stoichiometry of complexation I2/BDSAK is 1：1.Stability constants have been calculated in various temperatures and thermodynamic parameters have also been determined from the temperatures dependence of the stability constants by using van＇t Hoff equation.The results indicate the iodine complex with BDSAK is enthalpy stabilized but entropy destabilized.     

Green-Light Electroluminescence of Conjugated Copolymer Containing p-Phenylene-ethynylene and Oxadiazole

IntroductionSince the first report,in 1 990 ,of the electro-luminescence of the conjugated polymers in the filmof poly(p- phenylenevinylene) (PPV) sandwichedbetween an anode and a cathode of appropriatework functions[1] ,enormous efforts have been de-voted to the synthesis of light emitting poly-mers[2— 4 ] .Having been found potential applicationof conjugated polymers in photoluminescence(PL)and electro- luminescence (EL ) ,their importantproperties,polymer processability,band gap tun-abil…     

A Novel Copper（Ⅱ） Coordination Polymer with Figure-of-eight-shaped Channels Occupied by Flexible Monodentate and Bidentate N,N＇-bipyrdyl Ligands

A copper（Ⅱ） coordination polymer, [Cu3（HOA）2（bpp）4]n （1, HnOA = 3,3＇,4,4＇- oxidiphthalic acid, bpp = 1,3-bis（4-pyridyl） propane）, has been hydrothermally synthesized. The crystal structure is of monocl...     

THE SYNTHESIS AND CHARACTERIZATION OF Ba-CROSSLINKED POLYMER ANTI-RADIATION MATERIALS

Crosslinked poly(methyl methacrylate) and polystyrene with barium dimethacrylate [Ba(MA)_2] as crosslinking agent have been synthesized. The relationship between X-ray absorbability and the content of Ba(MA)_2 in polymers was investigated. TGA and DSC results indicated that the crosslinked polymers containing barium dimethacrylate have a much better heat stability than pure PMMA or PS. The mechanical properties of the polymers containing barium are improved in comparison with the pure PMMA.     

Synthesis and in vitro Property Study of Polyaspartamides

Cationic polyaspartamides including poly-α,β-[N＇-（2-aminoethyl）-L-aspartamide] （PAEA）, poly-α,β-[N＇-（4- aminobutyl）-L-aspartamide] （PABA）, poly-α,β-[N＇-（6-aminohexyl）-L-aspartamide] （PAHA）, poly-α,β-[N＇-（5-amino- 3-azapentyl）-L-aspartamide] （PAAPA） and poly-α,β-[N＇-（8-amino-3,6-diazaoctyl）-L-aspartamide] （PADAOA） were synthesized from polysuccinimide. Their properties were evaluated by ^1H NMR, IR, GPC, fluorescence measurement and in vitro cytotoxicity assays. The molecular weights per primary amine charge group of PAEA（1） （Mn= 2229）, PAAPA and PADAOA are 212, 279, and 226. Polyaspartamides including PAEA（1）, PAAPA, PADAOA and low molecular weight PAHA are markedly less toxic than poly（ethyleneimine） and poly（L-lysine）, however, PABA and higher molecular weight PAHA are slightly less toxic than poly（L-lysine）. Cell cytotoxicity of PAHA was seen to decrease with increasing molecular weight of PAHA, due to water solubility reduction. The negatively charged plasmid DNA has been found to be completely neutralized and complexed by the cationic polyaspartamides at an N/P ratio of 5 ： 1 to 10 ： 1, forming self-assembled polyplexes via ionic interactions. These polyaspartamide/DNA complexes possess stable zeta potentials and mean particle diameters of about 180 nm for PAEA （1）/DNA and PAAPA/DNA complexes and 280 nm for PADAOA/DNA complexes.     

SYNTHESIS OF CHIRAL CONJUGATED POLYBINAPHTHYLS BY SONOGASHIRA REACTION

Chiral polymers P-1 and P-2 were synthesized by the polymerization of （R）-3,3＇-diiodo-2,2＇-bisbutoxy-1,1＇- binaphthyl （M- 1 ） with 2,5-di（4-ethynylphenyl）- 1,3,4-oxadiazole （M-3） and （R）-3,3＇-diethylnyl-2,2＇-bisbutoxy- 1,1 ＇-binaphthyl （M-2） with 1,2-di（4-bromophenyl）acetylene （M-4） under Sonogashira reaction, respectively. Both monomers and polymers were analyzed by NMR, MS, FT-IR, UV-Vis spectroscopy, DSC-TGA, fluorescence spectroscopy, GPC and CD spectroscopy. CD spectra of P-1 and P-2 are similar due to the same chiral center units and main chain structure. The long wavelengths CD effect of P-1 and P-2 can be regarded as the more extended conjugated structure and a highly rigid backbone in the polymer chain. Polymers have strong blue fluorescence due to the efficient energy migration from the extended n-electronic structure of the polymers to the chiral binaphthyl core and are expected to provide understanding of the relationship between molecular structure and fluorescent property of the chiral polymers.