Synthesis, Structure And Surface Photo-electric Property Of Ni(Ⅱ) Complexes

Ten Ni（II） coordination complexes were obtained by hydrothermal synthesis method ofNi（II） with1,2,4,5-benzenetetra-carboxylic acid,1,3,5-benzenetri-carboxylate acid, Citicacid, maleic acid and pyrazole. There are five Ni（II） polymers（chapter Three）, and five Ni（II）supramolecules（chapter Four）. And two V（V） polymers have been synthesized（chapter Five）.There are seven complexes have been synthesized and characterized by myself, the other fivecomplexes were synthesized and characterized by our group people, in order to compare anddiscuss, they have been put in reported papers write by me. The structures of these complexeswere determined by single crystal X-ray diffraction, characterized by IR and UV-Vis spectra,elemental analyses and surface photovoltage spectroscopy（SPS）, compare and discuss itssurface photo-electric property.1. The molecular formula of complexes:（1）[Ni（btec）（phen）·（H₂O）₂]_n（7）[Ni（HL2）₂]（2）[NiCd₂（Hcit）₂H₂O]_n（8）[Ni（pdc）₂（Hppz）₂]·H₂O（3）[NiCd（L1）₂（H₂O）₄]_n（9）[Ni（mal）（phen）（H₂O）₂]（4）[Ni₂Cd（C₈H₃O₅）₂（H₂O）₂]_n（10）[Ni（otpha）（Imh）₃（H₂O）₂]·H₂O（5）[NaNi（NTA）（H₂O）]_n（11）[CoV₂（phen）（H₂O）O₆]_n（6）[Ni（Pz）₄（H₂O）₂·（H₂btc）₂·H₂O]（12）[CuV2（phen）（H₂O）O₆]_n（btec=1,2,4,5-benzenetetra-carboxylic acid, phen=1,10-phenanthroline, Hcit=Citicacid, H₂L1=2-（1-pyrazol）-succinic acid）, C₈H₃O₅=2-Hydroxy-1,3-Benzenedicarboxylicaacid, NTA=Ammonia triacetic acid, Pz=pyrazole, btc=1,3,5-benzenetri-carboxylate acid,H₂L2=2-（1-piperazinl）-succinic acid), pdc=pyridine-2,5-dicarboxylic acid, ppz=piperazine, mal=malonic acid, otpha=phthalic acid, Imh=tmidazole)2. Complex （1） is a2D Ni（II） coordination polymer bridged by btec groups; complexes（2）-（5） are Ni（II） and Cd（II） hetero-metallic polymers, infinite are2D,1D,1D and3Drespectively; complexes （6）-（10） are Ni（II） mononuclear complexes, and bridged to2D,3D,3D,3D and1D supramolecule by hydrogen bonds.3. Complex （11） and （12） are V（V） hetero-metallic polymers. In molecular formulas, allatoms are same except one transition-metal cation, but there are a little difference in crystalstructure, all bridged by O atoms, form2D and1D polymers.4. The photo-electric properties of complexes were investigated by surface photovoltagespectroscopy（SPS）. The results of SPS show that the three complexes exhibit obviousphotovoltage responses in the range of300⁸00nm, which indicates that they all possesscertain photo-electric conversion properties. 5. Comparing and analyzing the SPS results of these complexes, it can be found that thecomponent, structure and dimensionality of complex, the category of ligand, the species andnumber of the direct coordination atoms as well as change of the coordinationmicroenvironment of central metal Ni（II） ion all affect obviously the SPS responses. The SPSand UV-Vis spectra of the complexes were interrelated.