Tetrathiafulvalene radical cation dimerization in a bistable tripodal [4]rotaxane

被引:59
作者
Aprahamian, Ivan [2 ,3 ]
Olsen, John-Carl [1 ]
Trabolsi, Ali [1 ]
Stoddart, J. Fraser [1 ]
机构
[1] Northwestern Univ, Dept Chem, 2145 Sheridan Rd, Evanston, IL 60208 USA
[2] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
[3] Univ Calif Los Angeles, Calif NanoSyst inst, Los Angeles, CA 90095 USA
关键词
bistability; click chemistry; dimerization; rotaxanes; template synthesis;
D O I
10.1002/chem.200800191
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The template-directed synthesis of a bistable tripodal [4]rotaxane, which has cyclobis(paraquat-p-phenylene) (CBPQT(4+)) as the pi-electron-deficient rings, and tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene units as the pairs of pi-electron-rich recognition sites located on all three legs of the tripodal dumbbell, is described. The chemical and electrochemical oxidation of the [4]rotaxane and its tripodal dumbbell have allowed us to unravel an unprecedented TTF center dot+ radical cation dimerization. In fact, two types of TTF dimers, namely, the radical cation dimer [TTF center dot+], and the mixed-valence one [(TTF)(2)](center dot+), have been observed at room temperature for the tripodal dumbbell, whereas, in the case of the [4]rotaxane, only the radical cation dimer [TTF center dot+](2) is formed. This anomaly can be explained if it is accepted that most of the neutral TTF units in the [41rotaxane are encircled by CBPQT(4+) rings, which renders the formation of the mixed-valence dimer [(TTF)(2)](center dot+) highly unfavorable.
引用
收藏
页码:3889 / 3895
页数:7
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