A novel strategy to construct Janus metallamacrocycles with both a Ru-arene face and an imidazolium face

作者：Li, Ji; Zhang, Peipei; Xu, Yan; Su, Zhi; Qian, Yong^*; Li, Shunli; Yu, Tao^*; Sadler, Peter J.^*; Liu, Hong-Ke^*

来源：Dalton Transactions, 2017, 46(46): 16205-16215.

DOI：10.1039/c7dt03374e

• EFFECTIVE CORE POTENTIALS
• ASYMMETRIC HYDROGENATION
• MOLECULAR CALCULATIONS
• ANTICANCER ACTIVITY
• CARBENE LIGANDS
• COMPLEXES
• DNA
• RECOGNITION
• RUTHENIUM(II)
• TEMPERATURE

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 CH2Cl2 or CH2Br2 to generate the novel mononuclear metallamacrocyclic [RuX(arene) L2CH2]X-3 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 (CH2Cl2 or CH2Br2) that links the two arms of an initially formed non-cyclic complex (arene) RuX2L2 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.

• 出版日期2017-12-14
• 单位南京师范大学