| Ten new novel complexes have been synthesized by the hydrothermal reaction of Co（Ⅱ）and Fe（Ⅱ） with Pyrazine-2,3-dicarboxylic acid, Imidazole-4,5-dicarboxylic acid etc.Complexes （1）-（10） were obtained single crystals. Complexes were characterized by singlecrystal X–ray diffraction, surface photovoltage spectroscopy （SPS）, IR spectra and UV–Visspectra, discussed the relations structure and photo-electric properties of complexes,comparative analysis of the SPS and UV-Vis, obtain some regularity results. In addition, Inorder to better contrast and study photo-electric properties of the complexes, in thearrangement of teacher, other students of our group synthesized several correlative complexes（not published）（complexes （11）-（18）） were tested X-ray powder diffraction（XRD）,thermogravimetric analysis（TG）. Investigate their relationship with SPS. Then wecomparative analysis of different complexes photo-electric properties conversion, especiallyutilize ray radiation scope and photo-electric conversion efficiency. The molecular formulasare as follows:（1）[Co（2,3-pzc）·2H2O]n·2nH2O （11）[Co（o-phta）（Pz）2]n（2）[Co（HImbc）2·（H2O）2]（12）[Co（PTA）2（Imh）2]·（PTA）·H2O（3）[Co（2-pdc）3·H2O]（13）{[Co（pdc）2（H2O）]·（Pz’）·2H2O}n（4）[Co（3-pdc）2·（H2O）4]（14）[K2Co2（ox）（btec）（CH3OH）2]n（5）{[Fe（Hpdc）2（H2O）2]·2H2O}（15）{[Ni（bipy）（H2O）4]·（bdc）}（6）[Fe（HImbc）2·（H2O）2]（16）[Ni（PhCOO）（phen）（H2O）3]·（PhCOO）（7）[Fe（pdc）·（H2O）2]n·n H2O （17）[Ni（dcpz）（H2O）4]（8）[Fe（ox）·（H2O）]n（18）[Ni（pic）2（H2O）2]（9）[ⅠCdⅡ0.25Cd0.5Na0.5（btec）0.5（H2O）2]n（10）[ⅠCdⅡCd （btec）]n·5H2O（2,3-pzc=Pyrazine-2,3-dicarboxylic acid，Imbc=Imidazole-4,5-dicarboxylic acid，2-pdc=pyridine-2-dicarboxylic acid，3-pdc=Nicotinic acid，H2pdc=pyridine-2,5-dicarboxylic acid,H2（ox）=oxalic acid, H4btec=1,2,4,5-benzenetetracarboxylic acid, H2-phta=o-phthalic acid,Pz=pyrazole, HPTA=Phonyl-toluic acid, Pz’=piperazine, Imh=tmidazole, H2bdc=m-phthalicacid, PhCOO=benzoate, H2dcpz=pyrazole-3,5-dicarboxylic acid, Hpic=2-pyrazinecarboxylicacid, bipy=2,2’-bipyridine, phen=1,10-phenanthroline） We emphatically adopt the SPS method to explore photo-electric properties of thecomplexes. Then they were compared and analysis with their UV–Vis. The results are listedas follows:1. Brief introduction of complexes structure:①A series of Co complexes, Complexes （1）,（2） and （4） are Co（Ⅱ）, complexes （3） isCo（Ⅲ）, the complex （1） is1D infinite chain bridged by2,3-pzc. Complex （2）,（3） and （4） ismononuclear complexes, further bridged to3D infinite structure by hydrogen bonds.Complexes （11）-（14） are Co（Ⅱ） polymers and supramolecles. Complex （11） is1Dcoordination polymer bridged by o-phta and further connected into2D supramolecule byhydrogen bonds. Complex （12） is a mononuclear complex with the ligand of PTA and Imhgroups and further connected into2D structure by hydrogen bonds. Complex （13） is1Dcoordination polymer bridged by pdc2-groups and further connected into2D structure byhydrogen bonds. Complex （14） is3D coordination polymer bridged by btec4-and ox2-groups.②A series of Fe complexes, Complexes （5）-（8） is Fe（Ⅱ） complexes, in which thecomplexes （5） and （6） are mononuclear structure, bridged to2D,3D infinite supramolecularby different types hydrogen bonds; complex （7） is2D polymer bridged by pdc2-, and futherbridged to3D infinite structure by hydrogen bonds. Complex （8） is1D infinite chain bridgedby the ox2-, and futher bridged to3D network structure by hydrogen bonds.③A series of Ni complexes, Complexes （15）-（18） are Ni （Ⅱ） mononuclear complexes,further bridged to1D,2D or3D infinite structure by hydrogen bonds.2. The comparative and analysis of SPS and UV–Vis of every series of complexes:①The complexes shows that there are photovoltage responses in the range of300800nm, which reveals they all possess photo–electric conversion properties.The SPS areassociated with the UV–Vis absorption spectra.②The central metal atoms is different, dnelectronic behavior is also different, so, theSPS is visible difference.③The center for the same metal complexes:a. The direct coordination atom are different, significantly affect the load transfertransition （LMCT） caused the band to band photovoltaic response number. For example: inthe series of Fe complexes, complex （8） in the direct coordination atom of O atoms,coordination model for FeO6, in the complexes （5）-（7）, direct coordination atom of N and Oatoms, coordination mode respectively, FeN2O4, FeN2O4, FeNO5, observation they werefound by SPS, complex （8） have one photovoltaic response with the band to bandphotovoltaic response; complexes （5）-（7） have two photovoltaic responses with band to bandphotovoltaic response. A series of Co complexes （11）14 also have similar regularity. b. The center metal coordination number is different, the crystal field is different, and thephotoelectric response is also different. Such as: the sixth chapter series Co complexes,complexes （11）-（12） for four-coordinated, in aberrations Td field, d-d*transition absorptionbands of Co（Ⅱ）:4A2'4T1（P）,4A2'4T1（F）,4A2'4T2. Complexes （13）-（14） forsix-coordinated, at the approximate Oh field, d-d*transition absorption bands of Co（Ⅱ）:4T1g（F）'4A2g,4T1g（F）'4T1g（P）,4T1g（F）'4T2g.c. The coordination micro environment is different, for d'd*transition induced by thephotovoltaic response also has significant impact. For example: Co（Ⅱ） is four-coordinated（Tdconfiguration） in （11） and （12）, and the d'd*transition response bands is red-shiftedthan that of （13） and （14）（six-coordinated）, because splittienergy of d orbit in Tdfield （Δt） areless than that in Ohfield （Δo）. |
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