Redox induced reversible structural transformations of dimeric and polymeric phenanthroline-based copper chelates

被引:17
作者
Bernhard, S [1 ]
Takada, K [1 ]
Jenkins, D [1 ]
Abruña, HD [1 ]
机构
[1] Cornell Univ, Dept Chem & Chem Biol, Baker Lab, Ithaca, NY 14853 USA
关键词
D O I
10.1021/ic010608o
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The synthesis and characterization of copper complexes of the phenanthroline based bridging ligands, 9-methyl-2-(2-{4-[2-(9-methyl-1,10-phenanthrolin-2-yl)ethyl]phenyl}ethyl)-1,10-phenanthroline, 1, and 1,12-bis(9-methyl-1,10-phenanthroline-2-yl)dodecane, 2, are presented. Whereas in the first case a discrete dimeric complex [Cu(2)(1)(2)](BF(4))2 was formed, in the latter, a coordination polymer [2(Cu(2))(n)](BF(4))(n) resulted. Both of these materials have been characterized by cyclic voltammetry (CV), the electrochemical quartz crystal microbalance (EQCM), and UV-vis spectroscopy and the results compared to those of the monomeric [Cu(dMP)(2)](BF(4)) (dmp is 2,9-dimethyl-1,10-phenanthroline) species. Oxidation of the dimeric species results in its precipitation and reduction results in stripping of the deposited layer as ascertained from CV and EQCM measurements. The electrooxidation of the copper centers in the coordination polymer results in changes in the coordination which are fully reversible upon reduction. The dissociation/regeneration of the coordination polymer as a function of the redox state of the copper centers has been characterized by CV, EQCM, and UV-vis spectroelectrochemistry.
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页码:765 / 772
页数:8
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