1. A novel strategy to construct Janus metallamacrocycles with both a Ru–arene face and an imidazolium face.
- Author
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Li, Ji, Zhang, Peipei, Su, Zhi, Qian, Yong, Li, Shunli, Liu, Hong-Ke, Xu, Yan, Yu, Tao, and Sadler, Peter J.
- Subjects
RUTHENIUM compounds ,IMIDAZOLES ,ANTINEOPLASTIC agents - Abstract
The bottom-up construction of highly functional metallamacrocycles from simple building blocks is a challenge of much current interest. We have used solvothermal reactions of a bifunctional p-bitmb ligand with [Ru(arene)X
2 ]2 in CH2 Cl2 or CH2 Br2 to generate the novel mononuclear metallamacrocyclic [RuX(arene)L2 CH2 ]X3 complexes 1–3 (1, arene = p-cym, X = Cl; 2, arene = bip, X = Cl; 3, arene = p-cym, X = Br), which were characterized by various techniques. These complexes are “bowl-like” and have two faces: one coordinative Ru centre (arene)Ru(N,N)X bridged by L (L = 1,4-bis(imidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene, p-bitmb) to a dipositive bis-imidazolinium centre. Cl− or Br− anions can be trapped inside the cavity of the “bowl-like” structure, forming H-bonds with the backbone. Experimental (NMR and ESI-MS) and computational (DFT calculations) studies show that the source of the bridging –CH2 – group is the dihalogenated solvent (CH2 Cl2 or CH2 Br2 ) that links the two arms of an initially formed non-cyclic complex (arene)RuX2 L2 by a mechanism of nucleophilic substitution. Optimization of the reaction conditions afforded the macrocyclic complexes in almost quantitative yields. The applications of these complexes as anti-proliferative agents towards cancer cells and for selective anion sensing have been explored. [ABSTRACT FROM AUTHOR]- Published
- 2017
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