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钱勇博士和刘红科教授课题组在DALTON TRANSACTIONS发表研究论文

发布时间:17-12-19 16:31:44 文章来源:化科院 浏览次数: [ 字号:


A novel strategy to construct Janus metallamacrocycles with both a Ru-arene face and an imidazolium face
Li, J (Li, Ji)[ 1 ] ; Zhang, PP (Zhang, Peipei)[ 1 ] ; Xu, Y (Xu, Yan)[ 1,2 ] ; Su, Z (Su, Zhi)[ 1 ] ; Qian, Y (Qian, Yong)[ 1 ]*(钱勇); Li, SL (Li, Shunli)[ 1 ] ; Yu, T (Yu, Tao)[ 3 ]* ; Sadler, PJ (Sadler, Peter J.)[ 4 ]*; Liu, HK (Liu, Hong-Ke)[ 1 ]*(刘红科)

[ 1 ] Nanjing Normal Univ, Coll Chem & Mat Sci, Jiangsu Collaborat Innovat Ctr Biomed Funct Mat, Nanjing 210046, Jiangsu, Peoples R China
[ 2 ] Nanjing Tech Univ, Coll Chem & Chem Engn, Nanjing 210009, Jiangsu, Peoples R China
[ 3 ] Tennessee Technol Univ, Dept Chem, 1 William L Jones Dr, Cookeville, TN 38505 USA
[ 4 ] Univ Warwick, Dept Chem, Gibbet Hill Rd, Coventry CV7AL, W Midlands, England

DALTON TRANSACTIONS,201712,46(46),16205-16215

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.


文章链接:
http://pubs.rsc.org/en/Content/ArticleLanding/2017/DT/C7DT03374E#!divAbstract
 


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