Deng Zhao-Xiang, Li Libo, Li Yadong
Department of Chemistry and the State Key Laboratory of Atomic and Molecular Nanosciences (Ministry of Education, China), Tsinghua University, Beijing 100084, People's Republic of China.
Inorg Chem. 2003 Apr 7;42(7):2331-41. doi: 10.1021/ic025846d.
A novel class of inorganic-organic-layered structures, CdE.0.5en (E = S, Se, Te; en = ethylenediamine), were obtained through reactions between elemental S, Se, or Te and Cd(2+) at appropriate solvothermal temperatures. These compounds contain atomic sheets of inorganic CdE frameworks spaced by ethylenediamine molecules, which serve as bridged ligands between two Cd atoms in neighboring inorganic layers and also prevent these inorganic slabs from collapsing and condensing into the bulk CdE phase. From the structural viewpoint, the essential mechanism for the formation of CdE nanorods in ethylenediamine-mediated solvothermal synthesis and the unique striated morphologies of the CdE products obtained through post-hydrothermal treatment of the CdE.0.5en layered precursors were revealed. The structure-selective crystallization of II-VI compound semiconductors in ethylenediamine under conditions of direct solvothermal synthesis or during the postconversion of the layered precursors was also explained on the basis of the similarity in atomic connectivity between the inorganic slabs in the precursors and those in wurtzite or zinc-blende phases. In addition, the CdE.0.5en precursors, which possess strong quantum-confinement effects resulting from their special inorganic-organic structures with alternating CdE and ethylenediamine layers, provide further possibilities of tailoring their electronic, magnetic, and optical properties through the structural modification of either the inorganic or the organic components.
通过元素硫、硒或碲与镉离子在适当的溶剂热温度下反应,获得了一类新型的无机 - 有机层状结构CdE·0.5en(E = S、Se、Te;en = 乙二胺)。这些化合物包含由乙二胺分子隔开的无机CdE骨架原子片层,乙二胺分子作为相邻无机层中两个镉原子之间的桥连配体,还能防止这些无机板层坍塌并凝聚成块状CdE相。从结构角度揭示了在乙二胺介导的溶剂热合成中形成CdE纳米棒的基本机制,以及通过对CdE·0.5en层状前驱体进行水热处理获得的CdE产物独特的条纹形态。基于前驱体中无机板层与纤锌矿或闪锌矿相中的无机板层在原子连接性上的相似性,还解释了在直接溶剂热合成条件下或层状前驱体后转化过程中,II - VI族化合物半导体在乙二胺中的结构选择性结晶。此外,CdE·0.5en前驱体因其具有由交替的CdE和乙二胺层组成的特殊无机 - 有机结构而具有很强的量子限域效应,通过对无机或有机组分进行结构修饰,为定制其电子、磁性和光学性质提供了更多可能性。