| Based on the photo-electrical conversion of solar energy,this paper designs and synthesizes the new-types of polymer-type photo-electric conversion molecular materials,to study the influence of structure on photoelectric performance and explore the relationship between the structure and function.First,five polymers with novel structures are designed and synthesized using the in situ ligand synthesis strategy:the novel polymers(1)-(3)containing L-type dicarboxylic acid ligands(H2L1,H2L2)are designed and synthesized using maleic acid and organic molecules containing N-H groups(phenylpiperazine,3,5-dimethylpyrazole)as precursor ligands through the aza-Michael addition reaction;two coordination polymers(4)and(5)based on 2-hydroxysuccinic acid are designed and synthesized by in situ hydroxylation reaction with fumaric acid,1,2,4-triazole as ligands.Secondly,coordination supramolecular compounds(6)-(12)based on transition metals dn(n=5,7,8,9,10)are synthesized with nitrogen-containing heterocyclic carboxylic acid as ligands.The molecular formulas of polymers are determined and analyzed by X-ray single crystal diffraction.(1)[Co(L1)(H2O)2]n(7)[Cu(4-pda)2(H2O)4]·H2O(2){[Ni(L1)(H2O)2]?H2O}n(8)[Mn(4-pda)2(H2O)4]·H2O(3){[Zn(L2)(H2O)2]?H2O}n(9)[Co(pzpmc)2(H2O)2]·H2O(4){[Cu2Cd0.5(trz)(hsuc)(fum)0.5(H2O)·2H2O]}n(10)[Ni(pzpmc)2(H2O)2]·H2O(5){[Cu2.5(trz)(hsuc)(fum)0.5(H2O)·2H2O]}n(11)[Co(3-pzc)2(H2O)2](6)[Zn(4-pda)2(H2O)4]·H2O(12)[Ni(3-pzc)2(H2O)2](H2L1=2-(phenylpiperazinyl)-succinic acid,H2L2=2-(3,5-dimethylpyrazol)-succinic acid,Htrz=1,2,4-triazole,H3hsuc=2-hydroxysuccinic acid,H2fum=fumaric acid,4-Hpda=3-(4-pyridyl)acrylic acid,Hpzpmc=pyrazole[1,5-a]pyrimidine-3-carboxylic acid,3-pzc-=pyrazole-3-carboxylate)Structural analysis shows that the polymers(1)-(3)have 1D infinite chain structures constructed by coordination bonds,polymers(4)and(5)have 2D infinite layered structures.(6)-(12)are mononuclear complexes constructed with nitrogen-containing heterocyclic carboxylic acid as ligand,which is connected into 2D structure by hydrogen bond.The IR,Uv-Vis-NIR,SPS,FISPS,XRD and TG of twelve polymers are tested and analyzed.Based on the structure,the relationship between the structure of the polymers and its surface electron behavior by the inducement of visible light is discussed.Concluding:(1)In the range of 300-800 nm,twelve polymers have a wide photovoltaic response band,which indicates that they have a certain photo-electric conversion properties;(2)The kinds of center metal can affect the photovoltaic response intensity and scope of the same structure of the polymers;(3)The conjugation degree of the ligands affect the photo-electric properties of the polymers.The increase of conjugation degree of ligands is beneficial to electron delocalization,broadening the light absorption range of polymers to the visible region,thus increasing the probability of electron transition in the ligands,facilitating the transmission of photogenerated carriers,and leading to the enhancement of photovoltaic response band strength. |
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