Construction of metal sandwich systems derived from assembly of silver(I) complexes with polycyclic aromatic compounds
Construction of metal sandwich systems derived from assembly of silver(I) complexes with polycyclic aromatic compounds
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DOI：
10.1021/ja983950h
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发表时间：
1999-06-02
影响因子：
15
通讯作者：
Maeno, N
中科院分区：
文献类型：
--
作者：
Munakata, M;Wu, LP;Maeno, N
以高氯酸银（I）与荧蒽（L-1）、苯并[ghi]芘（L-2）、[2，2]对环蕃（L-3）、癸环烯（L-4）反应，合成了一类新型的银夹心金属配合物。使用多环芳族化合物作为构建有机金属夹层体系的替代方法的想法是将金属离子的可塑性与烃的平面性和配位多样性联合收割机结合起来。单晶X射线衍射的结构研究表明，所有化合物都含有扩展的一维至三维结构，其中几个金属原子夹在两个稠合的多环系统之间。配合物1 [Ag-3（L-1）（2）（ClO 4）（3）]以二维W型结构存在于固体中，其中AgClO 4层被两层碳氢化合物隔开，配合物2 [Ag（L-2）（ClO 4）]（4）。甲苯含有两个通过广泛的芳族π-π堆叠偶联的双层聚合物链。在[Ag（L-3）（ClO 4）] 3中观察到柱撑砖状夹层骨架，而在[Ag-2（L-3）（ClO 4）（2）（benzene）] 4中观察到多层夹层骨架，使人联想到梯形。L-1的结构已被重新确定和L-2的报告，结构数据用于讨论银-π相互作用。电化学行为和ESR谱与体系中有机自由基物种的形成相一致。目前的研究结果可能代表一种替代的方法预先设计的多层体系的有机金属化学。
A new class of metal sandwich complexes of silver derived from silver(I) perchlorate and fluoranthene (L-1), benzo[ghi]perylene (L-2), [2,2]paracyclophane (L-3), and decacyclene (L-4) 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 hydrocarbons. 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 polycyclic systems. While complex 1, [Ag-3(L-1)(2)(ClO4)(3)], exists in the solid state as a two-dimensional W-type architecture in which AgClO4 layers are separated by two sheets of hydrocarbon, complex 2, [Ag(L-2)(ClO4)](4). toluene, contains two double-decker polymeric chains coupled via extensive aromatic pi-pi stackings. Pillared brick sandwiched framework was observed in 3, [Ag(L-3)(ClO4)], whereas the multidecker sandwich complex 4, [Ag-2(L-3)(ClO4)(2)(benzene)], is reminiscent of ladder. The structure of L-1 has been redetermined and that of L-2 reported; the structural data are used for discussion of the silver-pi interactions. The electrochemical behavior and ESR spectra are consistent with formation of the organic radical species in the system. The present findings may represent an alternative approach for predesigning the multilayered systems in organometallic chemistry.