| Project/Area Number |
10440201
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Kinki University |
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Principal Investigator |
MUNAKATA Megumu KINKI UNIVERSITY, DEPARTMENT OF CHEMISTRY, PROFESSOR, 理工学部, 教授 (80090942)
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| Project Period (FY) |
1998 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥13,600,000 (Direct Cost: ¥13,600,000)
Fiscal Year 1999: ¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 1998: ¥8,600,000 (Direct Cost: ¥8,600,000)
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| Keywords | aromatic compound / multilayered structure / metallocyclophane / coordination polymer / conductor / supermolecule / π-π interaction / silver complex / 有機金属化合物 / Ag錯体超分子 / 密度汎関数法 / 二重結合距離 |
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| Research Abstract |
A new class of sandwich and mutilayered silver(I) complexes derived from silver(I) perchlorate and fluoranthene(LィイD11ィエD1), benzo[ghi]perylene(LィイD12ィエD1), decacyclene(LィイD13ィエD1) and benzotriphenylene(LィイD14ィエD1) was prepared. The idea behind the use of polycyclic aromatic compounds as an alternative approach for construction of organometallic sandwich systems is to combine the plasticity of the metal ion and planarity and coordinative diversity of the hydorcarbons. Structural studies by single-crystal X-ray diffraction have shown that all compounds contain extended one- to three-dimensional structures in which several metal atoms are sandwiched between two fused polycylic systems. While complex AgィイD23ィエD2(LィイD11ィエD1)ィイD22ィエD2(ClOィイD24ィエD2)ィイD23ィエD2] exists in the solid state as a two-dimensional W-type architecture in which AgClOィイD24ィエD2 layers are separated by two sheets of hydrocarbon, the complex [AgィイD24ィエD2(LィイD12ィエD1)(ClOィイD24ィエD2)ィイD24ィエD2]・toluene, contains two double-decker polymeric chains coupled via extensive aromatic π-π stackings. The complex [AgィイD24ィエD2(LィイD12ィエD1)(ClOィイD24ィエD2)ィイD24ィエD2]・toluene, contains two double-decker polymeric chains coupled via extensive aromatic π-π stackings. The multideckeer sandwich complex [AgィイD22ィエD2(LィイD13ィエD1)(ClOィイD24ィエD2)ィイD22ィエD2)(benzene)] is reminiscent of ladder. The first metallocyclophane [Ag(LィイD14ィエD1)(ClOィイD24ィエD2)] (1) shows an interesting cyclophane-structure feature, the unusual aromatic interactions and a high conductivity. Especially it should be noted that in contrast to cylophanes such as [2,2]paracyclophane, benztriphenylene molecules in the metallocylophane 1 severely bend in ward by 0.35 Å with short intraplane distances to give columnar aromatic stack. The synthesis of the metallocyclophane may broaden insight into the new research field for functional materials and introduce a novel perspective in the area of supramolecular chemistry.
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