系列Cu(Ⅱ/Ⅰ)配聚物的合成、结构及光电性能

Syntheses,Structures and Photoelectron Property of a Series of Cu(Ⅱ/Ⅰ) Coordination Polymers

采用水热方法合成了3种Cu(Ⅱ/Ⅰ)配聚物及超分子,(1)[K2Cu2(ox)(btec)(MeOH)2]n,(2){[Cu(pdc)(H2O)2].H2O}n,(3)[Cu(cyan)(phen)].H2O(H2ox:草酸,H4btec:均苯四甲酸,MeOH:甲醇,H2pdc:2,5-吡啶二羧酸,phen:邻菲啰啉,Hcyan:氰尿酸).通过X射线单晶衍射、表面光电压光谱(SPS)、固体紫外-可见(UV-Vis)、傅里叶变换红外(FTⅠR)光谱、元素分析等方法对配合物进行了表征.结构解析结果表明,配合物(1)是具有三维(3D)无限结构的配聚物;(2)是具有二维(2D)无限结构的配聚物,但又通过氢键进一步连成了三维(3D)网络,(1)与(2)的中心金属均为Cu(Ⅱ)离子;(3)为含Cu(Ⅰ)的单核配合物,但又通过氢键和π-π堆积作用,使它成为2D超分子化合物.配合物SPS结果显示,配合物(1)-(3)在300-800nm范围内都呈现光伏响应,表明三者均具有一定的光电转换能力.讨论了配合物的组成、结构、维数、配体种类、中心金属离子价态及配位微环境对SPS的影响,并将SPS与UV-Vis光谱进行了关联.

Three Cu（II/I） coordination polymers/supramolecules were obtained by means of hydrothermal synthesis： （1） [K2Cu2（ox）（btec）（MeOH）2]n, （2） {[Cu（pdc）（H2O）2]？H2O}n, and （3） [Cu（cyan）（phen）]？H2O （where H2ox is oxalic acid, H4btec is 1,2,4,5-benzenetetracarboxylic acid, MeOH is methanol, H2pdc is pyridine-2, 5-dicarboxylic acid, phen is 1,10-phenanthroline, and Hcyan is cyanuric acid）. These compounds were characterized by single crystal X-ray diffraction, surface photovoltage spectroscopy （SPS）, solid phase ultraviolet-visible spectroscopy （UV-Vis）, Fourier transform infrared （FTIR） spectroscopy, and elemental analysis. Results indicated that （1） is a three-dimensional （3D） coordination polymer while （2） is a twodimensional （2D） coordination polymer connected into a 3D network through hydrogen bonding. For both （1） and （2）, the center metal is a Cu（II） cation. Compound （3） is a Cu（I） mononuclear complex which forms a 2D supramolecule via hydrogen bonding and π-π interactions. The SPS data for these three complexes exhibited photovoltage responses in the range of approximately 300 to 800 nm, indicating that all three possess some capacity for photoelectric conversion. The effects of composition, structure, dimensionality, ligands, valence states, and coordination environment of the central metal ions on the SPS results were investigated and discussed, as was the interrelationship between SPS and UV-Vis spectra.