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采用水热合成方法得到了3种Fe(Ⅱ/Ⅲ)配合物:[Fe2(μ2-btec)(μ2-H2btec)(phen)2(H2O)2]n(1),[Fe2(btec)(phen)2(H2O)4](2),{[Fe(o-pha)(phen)(H2O)]·H2O}n(3),(phen=1,10-phenanthroline,o-H2pha=o-phthalicacid,H4btec=1,2,4,5-benzenetetracarboxylicacid).X射线单晶衍射结果表明,配聚物(1)和配合物(2)都是以均苯四甲酸根做为桥,分别形成了1D和双核结构;配聚物(3)是以邻苯二甲酸根为桥形成了1D结构.3种配合物中羧基配位模式各不相同,在配合物(2)中,采用了μ2-η1η1η1η1配位模式;配聚物(3)中,邻苯二甲酸根的两个邻位的羧基采用了μ2-η2η1模式;而配聚物(1)中均苯四甲酸根存在两种不同的配位模式,一种为μ2-η1η1η1η1,另一种为两个对位羧基参与配位的μ2-η1η1模式.此外,分子间大量氢键的存在和π-π堆积作用又将3个配合物分别网成了3D和2D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.重点分析了3种配合物的表面光电压光谱,结果表明,它们在300～600nm范围内均有正的光伏响应,呈现出一定的p型半导体行为特征.而且由于3种配合物的结构、中心Fe离子的价态和Fe离子配位环境不同,使得3种配合物的SPS响应带的强度、位置和峰数都出现明显不同.此外,将SPS结果与其电子吸收光谱进行关联,发现它们基本上是一致的.
Three kinds of Fe (Ⅱ / Ⅲ) complexes were obtained by the hydrothermal method: [Fe 2 (μ 2 -btec) (μ 2 -H 2 btec) (phen) 2 (H 2 O) 2] n (phen) 2 (H2O) 4] (2), {[Fe (o-pha) phthalicacid, H4btec = 1,2,4,5-benzenetetracarboxylic acid). The results of X-ray single crystal diffraction show that both the polymer (1) and the complex (2) 1D and the binuclear structure, and the polymer (3) formed a 1D structure by the bridge of phthalates.The carboxyl coordination modes of the three complexes were different, and in the complex (2) η1η1η1η1 coordination mode; polymer (3), phthalates two adjacent carboxyl carboxyl group using μ2-η2η1 mode; and polymer (1) pyromellitic two different One is μ2-η1η1η1η1 and the other is the μ2-η1η1 mode in which the two carboxyl groups are coordinated.In addition, the presence of a large number of hydrogen bonds and the π-π stacking effect between the three complexes Respectively, into a 3D and 2D infinite structure. By infrared spectroscopy (IR), electron absorption spectroscopy (UV-Vis-NIR) and surface photovoltage spectroscopy (SPS) and other methods The surface photovoltage spectra of the three complexes were analyzed, and the results showed that all of them exhibited positive photovoltaic response in the range of 300-600 nm, showing a certain p-type semiconductor behavior. And because of the three kinds of coordination The structure, the valence state of the central Fe ions and the coordination environment of the Fe ions are different, so that the intensity, position and peak number of SPS response bands of the three complexes are obviously different.In addition, SPS results are correlated with their electron absorption spectra , Found that they are basically the same.