收稿日期: 2002-11-21
网络出版日期: 2003-01-18
Design and Synthesis of Nitrogen, Sulfur-Functional Group Based Ligands and the Structure of Related Coordination Supramolecular Complexes
Received date: 2002-11-21
Online published: 2003-01-18
Supported by
supported by NNSFC(29825103) and Chinese Academy of Sciences(KZCX2-H3)
以结构化学指导新型金属-有机纳米器件的合理合成和物理性能研究,探索它们的自组装规律,共设计合成了12个含N、S及COO-基团的具有不同对称性和立体选择性的新颖大骨架多官能团柔性配体,以及由它们与金属离子自组装合成了18个新型金属-有机纳米笼、纳米管和配位聚合物,开辟了一条合成金属-有机纳米器件的新途经.其中,一个具有Oh对称的金属纳米笼,笼内体积超过1000 A3,可以同时容纳多种离子和小分子,是目前已测定单晶结构的金属纳米笼中容量最大的一个.而用金属离子把纳米管串联成的金属-有机纳米管则是国际上首例报道的结构有序无机-有机纳米管阵列;并创新性的采用低温溶剂热法合成了一个新颖的具有半导体和顺磁性质的Ni-巯基嘧啶二维层状聚合物和两个二维折叠格子状化合物;另外,用巯基嘧啶作为难溶盐CuCN的溶解模板,得到了国际上首例六角形CuCN大环化合物和另外一个新颖的类石墨层状CuCN化合物.过渡金属与多官能团配体通过配位键来驱动和引导自组装,形成具有均一尺寸和特定形状的金属-有机纳米器件,是当今化学与材料领域研究的前沿之一.而通过设计合成具有特定对称性和立体选择性的有机配体,并把它们与金属离子自组装形成具有纳米尺寸和特殊功能的纳米球和纳米管,更是在纳米科技、化学催化、分子吸附和光电磁等领域具有重要的科学意义和应用前景.
赵颖隽 , 曹荣 , 洪茂椿 . 新型含氮、硫、氧配体及其超分子化合物的设计合成[J]. 中国科学院大学学报, 2003 , 20(1) : 112 -116 . DOI: 10.7523/j.issn.2095-6134.2003.1.018
We have explored several ways to design and prepare nitrogen-, sulfur-functional-groups based on ligands and the structure of related coordinationsupramolecular complexeswith one-dimensional (1D) chains, two-dimensional (2D) and three-dimensional (3D) net-works having organic molecular components and/or metal-metal interactions by using transi-tion metal ions and organic ligands. Summarizes their syntheses, structures and properties,including conductivity and magnetic properties. The following aspects are discussed: (1) a se-ries of metal supramolecular complexes; (2) design and synthesis of the ligands based on nitro-gen-sulfur- and carboxylate-fuctional groups and the structures of related complexes; and (3)studies of series of copper cyanide complexes.
Key words： supramolecular complex; self-assembly; design and synthesis
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