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Synthesis of Discrete Polynuclear Complexes and Units for Metal-Assembled Compounds

离散多核配合物和金属组装化合物单元的合成

基本信息

批准号：
10149106
负责人：
OKAWA Hisashi
金额：
$ 44.74万
依托单位：
Kyushu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas (A)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2001
项目状态：
已结题

项目摘要

1) Heterodinuclear metal complexes of various combinations of metal ions were prepared using compartmental ligands and their physicochemical properties and functions were examined. Extensive magnetic studies were made for the complexes to reveal the significance of the electronic structures in determining the nature of magnetic interaction.2) Cyanide-bridged bimetallic compounds of various network structures were prepared and their magnetic nature was studied. Spontaneous magnetization occurs for 2-D and 3-D network compounds but not for 1-D compounds. [Mn(glya)]_3[Cr(CN)_6]_3 (glya=glycine amide) has a 3-D network based on a defective cubane structure and shows ferromagnetic ordering with Tc=71 K, that is the highest among molecular magnets so far structurally characterized.3) A new class of cluster compounds, comprising of 。ニorgano-metallic。ヌ unit and metal oxide unit, were prepared and their properties were studied. They include 。ニdouble bookshelf。ヌ type, 。ニwindmill。ヌ type, 。ニtriple cubane。ヌ type etc. and unique reactivities were found for some of them.4) Porous coordination polymers of various networks were designed by the combination of metal ions and an organic building ligand such as 4,4'-bipyridine. They function as a host for including quest molecules such as CH_4, CO_2, O_2 and N_2.5) Construction of covalently-linked linear metal clusters was studied and linear M-Mo-Mo-M (M=Rh, Ir) clusters were obtained by the reaction of Mo_2(pyphos)_4 (pyphos=6-dipenylphosphino-pyridonate) with M(I) complexes. The terminal metal is reactive due to coordinative unsaturation and some unique reactions were developed.6) Tetranuclear Fe(III) compounds of a cubane structure were prepared using tridentate alcoholic ligands and their magnetic properties were examined. The complex [Fe_4(sae)_4(MeOH)_4] (sae=salicylideneaminoethanolate) was found to be a single-molecule magnet based on various magnetic studies.

1)利用隔室配体制备了不同金属离子组合的异双核金属配合物，并对其物理化学性质和功能进行了研究。对配合物的磁性进行了研究，揭示了电子结构对磁性相互作用性质的重要性。2）制备了具有不同网络结构的氰根桥联双金属配合物，并对其磁性进行了研究。自发磁化发生在2-D和3-D网络化合物，但不为1-D化合物。[Mn（glya）]_3[Cr（CN）_6]_3（glya=glycine amide）具有基于立方烷缺陷结构的三维网络结构，具有铁磁有序性，Tc=71 K，是迄今为止结构表征最高的分子磁体。有机金属。制备了氧化物单元和金属氧化物单元，并对其性能进行了研究。它们包括。双层书架。字体，。风车。字体，。三倍立方烷。4）通过金属离子与有机配体如4，4 ′-联吡啶的结合，设计了具有不同网络结构的多孔配位聚合物。5）研究了共价连接的线型金属簇合物的构筑，通过Mo_2（pyphos）_4（pyphos=6-二苯基膦基吡啶酮）与M（I）配合物的反应，得到了线型M-Mo-Mo-M（M=Rh，Ir）簇合物。末端金属由于配位不饱和而具有活性，并发展了一些独特的反应。6）利用三齿醇配体合成了立方烷结构的四核Fe（III）化合物，并研究了它们的磁性。通过对配合物[Fe_4（sae）_4（MeOH）_4]（sae=水杨醛缩氨基乙醇）的磁性研究，确定其为单分子磁体。