State Key Laboratory of Molecular Engineering of Polymers, Department of Chemistry, Fudan University, Shanghai, 200433, P. R. China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, Shanghai, 200032, P. R. China.
Chemistry. 2019 Dec 5;25(68):15687-15693. doi: 10.1002/chem.201904196. Epub 2019 Nov 6.
A novel template-free Cp*Rh-based molecular Solomon link has been established through selection of the flexible ligand L as a linker and the half-sandwich rhodium(III) dinuclear fragment B1 as a rigid capping unit. Furthermore, we demonstrate that the self-assembly of the Solomon link based on the flexible ligand is both solvent- and concentration-dependent: the Solomon link is formed in concentrated methanolic solutions, whereas formation of a dinuclear trapezoidal rectangle is favored at low concentrations or in acetonitrile or DMF solutions. Remarkably, alteration of the solvent or concentration can promote a unique and dynamic interconversion between the two molecular species, accompanying conformational change of the ligand. The synthetic outcomes are supported by single-crystal X-ray diffraction analysis.
通过选择柔性配体 L 作为连接体和半三明治铑(III)双核片段 B1 作为刚性封端单元，建立了一种新型无模板 Cp*Rh 基分子 Solomon 链接。此外，我们证明了基于柔性配体的 Solomon 链接的自组装既受溶剂又受浓度的影响：在高浓度甲醇溶液中形成 Solomon 链接，而在低浓度或乙腈或 DMF 溶液中则有利于形成双核梯形矩形。值得注意的是，溶剂或浓度的改变可以促进两种分子物种之间的独特和动态相互转化，同时伴随着配体的构象变化。单晶 X 射线衍射分析支持了这些合成结果。
