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在水热条件下合成了两个Keggin型多金属氧簇构筑的有机无机杂化化合物:[CuⅠ(2,2’-bipy)2]{[CuⅠ(2,2’-bipy)2]2][PW12O40]}·4H2O(1)和{[(H3bpdc)3][PW12O40]·H2bpdc}·2H2O(2),并通过元素分析、红外光谱、热失重曲线和单晶X-射线衍射等手段确定了其组成和结构。化合物1属于单斜晶系,P2(1)/n空间群,化合物2属于三斜晶系P 1空间群。化合物1中2,2’-联吡啶-3,3’-二羧酸(H2bpdc)经原位脱羧反应形成{[CuⅠ(2,2’-bipy)2]2[PW12O40]}—阴离子和[CuⅠ(2,2’-bipy)2]+配位阳离子,并通过氢键和π-π堆积作用形成一维链状结构。化合物2中多酸阴离子和H2bpdc有机组分通过氢键和静电引力形成三维超分子网络。电化学研究表明,两种化合物都存在三步氧化还原过程。
Under hydrothermal conditions, two organic-inorganic hybrid compounds with Keggin type polyoxometalates were synthesized: [CuI (2,2’-bipy) 2] {[CuI (2,2’-bipy) 2] [PW12O40]} 4H2O (1) and {[(H3bpdc) 3] [PW12O40] · H2bpdc} · 2H2O (2) were determined by elemental analysis, IR, TG and single crystal X-ray diffraction Its composition and structure. Compound 1 belongs to the monoclinic space group P2 (1) / n and compound 2 belongs to the triclinic P 1 space group. The in situ decarboxylation of 2,2’-bipyridine-3,3’-dicarboxylic acid (H2bpdc) in compound 1 resulted in the formation of {[CuI (2,2’-bipy) 2] 2 [PW12O40] Cu Ⅰ (2,2’-bipy) 2] + coordinates with the cation and forms a one-dimensional chain structure through the hydrogen bonding and π-π stacking. Compound 2 polyacid anion and H2bpdc organic components through hydrogen bonding and electrostatic attraction to form a three-dimensional supramolecular network. Electrochemical studies show that both compounds have a three-step redox process.