系列含二核钼(钨)簇阴离子化合物的合成、结构特征和簇间相互作用  

Synthesis, Structural Feature and Intercluster Interaction of a Series of Compounds Containing Binuclear Molybdenum (Tungsten) Cluster Anion

作　　者：卢绍芳[1] 朱永宝[1] 梁玉仓[1] 余荣民[1] 黄小荥[1] 孙福侠[1] 吴锵金[1] 黄子祥[1] 

机构地区：[1]中国科学院福建物质结构研究所结构化学国家重点实验室,福州350002

出　　处：《化学学报》2004年第3期253-261,共9页Acta Chimica Sinica

基　　金：国家自然科学基金 (Nos.2 96730 4 6 ;2 97330 90 );福建省自然科学基金 (No.B960 1 8);结构化学国家重点实验室基金资助项目

摘　　要：报道了系列共 9个以 [(M2 OnS4-n) (i mnt) 2 ] 2 -(M =Mo ,W ;i mnt=S2 CC(CN) 2 -2 ;n =0 ,1,2 )二核簇为阴离子 ,以某些有机基团如R4N (R =烷基 ) ,质子化的 4,4′ bpy或碱金属Cs ,K ,二价金属Ni,Mn配合物为阳离子的新化合物的合成 ,晶体结构 ,谱学表征和成键特征 .这些化合物通过S…S ,S…Cl,Cl…Cl超分子相互作用及离子间氢键形成双聚、链状、层状、三维网络及包合物堆积结构 .采用扩展的H櫣ｃｋｅｌ近似下的紧束缚能带方法计算了部分化合物的能带结构 ,表明正是这些簇间或离子间的相互作用提供了簇间电荷转移的可能 .The syntheses, crystal structures and bonding features of a series of nine cluster compounds with [(M 2O nS 4-n)(i-mnt) 2] 2- (M=Mo, W; i-mnt=S 2CC(CN) 2- 2; n=0, 1, 2) as the cluster anion and some organic groups such as R 4N (R=alkyl), protonated 4,4′-bpy etc., or alkali metals Cs, K, or Ni(II), Mn(II)-centered complexes as the cation are systematically described. These compounds possess a dimeric, chain-like, layer-like or clathrate packing structure linked by S…S, S…Cl, Cl…Cl supramolecular interaction and interionic hydrogen bond. Their band structures are calculated by using tight-bind method within the extended Hückle scheme. The results show that it is the intercluster or interionic interaction that produces the possibility of the charge transfer between the clusters. The measurement of the temperature-change specific conductivity gives the evidence that these cluster compounds possess electroconductivity of semiconductor.

关 键 词：二核原子簇合物 钼离子 钨离子 阴离子 合成 晶体结构 簇间相互作用 半导体导电性能 能带分析 

分 类 号：O641[理学—物理化学]