Department of Chemistry and Key Laboratory of Organic Synthesis of Jiangsu Province, Soochow University, Suzhou 215123, PR China.
Inorg Chem. 2011 Aug 1;50(15):6972-8. doi: 10.1021/ic200157v. Epub 2011 Jun 29.
A series of supertetrahedral polymers of chalcogenometalates (T3 cluster compounds) integrated with M-phen complexes (phen =1,10-phenanthroline; M = Ni, Fe) was prepared by a similar solvothermal technique. Compound Fe(phen)(3)[H(4)In(20)S(38)]·Hphen·3HDMA·8H(2)O (Mp-InS-4) (DMA = dimethylamine) is a 1-D straight chain. Compounds M(phen)(3)[In(20)S(37)]·6Hphen·4H(2)O (M = Ni, Mp-InS-5; Fe, Mp-InS-6) are the first reported 2-D Tn polymers integrated with complex cations of M(phen)(3). Compound Ni(phen)(3)[H(4)In(20)S(38)]·2Hphen·2HDMA·3H(2)O (Mp-InS-7) shows a zigzag 1-D structure. We find that the reaction time is an important factor in assembling of the T3 clusters. Prolonging the reaction time seems favorable to the higher condensed phases (from 0-D to 2-D). However, a longer reaction time resulted in the crack of 2-D structure. Integrating M-phen complex cations with the chalcogenido anions can improve absorption of the materials in the visible range due to the charge transfers within the cations or between cations and anions.
一系列具有多硫属元素（T3 团簇化合物）和 M-菲咯啉配合物（phen = 1,10-菲咯啉；M = Ni, Fe）的超四面体聚合物是通过类似的溶剂热技术制备的。化合物Fe(phen)(3)[H(4)In(20)S(38)]·Hphen·3HDMA·8H(2)O（Mp-InS-4）（DMA = 二甲胺）是一维直线型。化合物M(phen)(3)[In(20)S(37)]·6Hphen·4H(2)O（M = Ni, Mp-InS-5；Fe, Mp-InS-6）是首例报道的二维 Tn 聚合物，其中整合了M(phen)(3) 配合物阳离子。化合物Ni(phen)(3)[H(4)In(20)S(38)]·2Hphen·2HDMA·3H(2)O（Mp-InS-7）表现为交错的一维结构。我们发现反应时间是组装 T3 团簇的一个重要因素。延长反应时间有利于形成更高凝聚相（从 0-D 到 2-D）。然而，更长的反应时间导致了 2-D 结构的破裂。将 M-菲咯啉配合物阳离子与硫属阴离子整合，可以通过阳离子内部或阳离子与阴离子之间的电荷转移来提高材料在可见光范围内的吸收。
