采用水热合成方法得到了3种Co(II)配合物: [Co(μ4-btec)0.5(phen)(H2O)]n (1), [Co2(μ4-btec)(bipy)2(H2O)2]n (2), [Co2(μ2-btec)(phen)2(H2O)4] (3) (phen＝1,10-phenanthroline, bipy＝2,2’-bipyridine, H4btec＝1,2,4,5-benzenetetracarboxylic acid). X射线单晶衍射结果表明: 3个配合物都是以均苯四甲酸根做为桥, 分别形成了2D, 1D和双核结构. 但在3种配合物中, 均苯四甲酸根的配位模式各不相同, 分别采用了μ4-η1η2η1η2, μ4-η1η1η1η1, μ2-η1η1η1η1配位模式. 此外, 分子间大量氢键的存在和π-π堆积作用又将3个配合物网成了3D无限结构. 通过红外光谱(IR)、电子吸收光谱(UV-Vis-NIR)及表面光电压光谱(SPS)等方法对配合物进行了表征. 3种配合物的表面光电压谱研究表明: 它们在300～600 nm范围内均有正的光伏响应. 将SPS与其电子吸收光谱进行关联, 发现它们基本上是一致的.

Three new mixed-ligand cobalt(II) complexes, [Co(μ4-btec)0.5(phen)(H2O)]n (1), [Co2(μ4-btec)- (bipy)2(H2O)2]n (2) and [Co2(μ2-btec)(phen)2(H2O)4] (3) (phen＝1,10-phenanthroline, bipy＝2,2’-bipyridine, H4btec＝1,2,4,5-benzenetetracarboxylic acid) have been hydrothermally synthesized and characterized by single crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic system, with P2(1)/c space group, a＝1.03364(4) nm, b＝1.05089(4) nm, c＝1.34413(7) nm, β＝105.8610(16)°; complex 2 belongs to triclinic system, P-1 space group, with a＝0.75689(8) nm, b＝0.89882(7) nm, c＝1.06594(12) nm, α＝80.325(7)°, β＝73.092(5)°, γ＝77.077(3)°; and complex 3 also belongs to triclinic system, P-1 space group, with a＝0.64331(13) nm, b＝0.99762(14) nm, c＝1.19864(17) nm, α＝84.193(6)°, β＝76.246(3)°, γ＝85.304(4)°. These three complexes are all bridged by the betc4－ ligands to form 2D, 1D and dinuclear structures. But the coordination modes of the betc4－ respectively adopt μ4-η1η2η1η2, μ4-η1η1η1η1, and μ2-η1η1η1η1 in the three complexes. The existence of hydrogen bonds and π…π type interactions make the complexes further connected to three-dimensional networks. The complexes were characterized by IR, UV-Vis-NIR and surface photovoltage spectra (SPS). The SPS of complexes 1～3 indicate that they all exhibit positive surface photovoltage (SPV) responses in the range of 300～600 nm. However, the intensity, position and numbers of SPV responses are different. The distinctions can be mainly attributed to their structures and coordination environments of the Co ions in the three complexes. Their SPS spectra were found to be basically agreed with their UV-Vis-NIR.