Series Ni(Ⅱ) Coordination Supermolecule Of Nitrogen Heterocyclic Carboxylic Acid:Design、Synthesis、 Structure And Photoelectric Property

Seven complexes have been synthesized by the hydrothermal methods of Ni(II), Co(II),Cu(II) and Cd(II) ion. There are three kinds of Ni(II) supermolecule complexes,a new Ni-Cdheteronuclear polymers, Co(II),Cu(II) and Cd(II) supermolecule complex every one. Thestructures of these complexes were determined by single crystal X-ray diffraction, Themolecular formula of complexes:(1)[Cu(C8H7O2)2Phen(H2O)](2)[Ni(C8H7O2)2Phen(H2O)](3)[Co(3-pydc)2(H2O)4](4)[Cd(3-pydc)2(H2O)4]（4）(5)[Ni(2-pzdc)2(H2O)4](6)[NiCd(C4H3O4)2(C3H3N2)2(H2O)4]n(7)[Ni(C3H3O4)2(C4H10N2)2](C8H7O2=p-toluylic acid、3-pydc=pyridine-3-dicarboxylic acid、2-pzdc=Pyrazine-2-dicarboxylic acid、 C4H3O4=fumaric acid、 Phen=1,10-phenanthroline、C3H3N2=parazole、C4H10N2=piperazidine)All single crystals were obtained and determined by X–ray single crystaldiffraction.Structur alanalyses show that Compounds (6) is1D chain polymer and other sixare supermolecule complexes. Compounds (1) and (2) forming the1D chain-likesupramolecular by hydrogen bond. Compounds (3)(4)(5)(7) forming3D networks byhydrogen bond.complex (6) is a1D chain-like polymer,which extend for3D hydrogen bondnetwork by the hydrogen bonding interaction between the adjacent chains.It was noteworththat Pyridine carboxylic acid ligands have decarboxylated in the reaction process.The structures of these complexes were determined by single crystal X-ray diffraction,characterized by IR and UV-Vis spectra, Thermogravimetric Analysis and surfacephotovoltage spectroscopy(SPS).The most important is contrast and research SPS.the resultsshowed as follows:(1) SPS detection show that the three complexes exhibit obviousphotovoltage responses in the range of300~800nm, which indicates that they all possesscertain photo-electric conversion properties.(2)The spatial structure of complex influence theintensity of SPS:(a) The dimension of the structure in polymers influence the intensity of SPS.For example,(2) and (7) are both Ni(II)0D supermolecule complexes. Compound (2)forming the1D chain-like, however, Compound (7) linked into3D networks supramolecularby hydrogen bond. The intensity of SPS is (7)>(2), which indicated that the structure of thehydrogen bond network may also influence the intensity of SPS without covalent bond.(b) The species and property of ligand in the complex has significant influence in the SPS. SPSresponse of coordination polymer was strengthen and widen due to conjugating organicligands, especially mixed organic ligands, obviously. For example, coordination polymers (2)is a complex with ligand Phen, the band intensity is stronger than complex (5).(c) The delectron configuration and number of central metal ion in complex has certain effect on theSPS number and position. In the same structure of the complexes with same ligands, theintensity of SPS are move to long wave.