Modular synthesis and dynamics of a variety of donor-acceptor interlocked compounds prepared by click chemistry

被引:84
作者
Braunschweig, Adam B.
Dichtel, William R.
Miljanic, Ognjen S.
Olson, Mark A.
Spruell, Jason M.
Khan, Saeed I.
Heath, James R.
Fraser Stoddart, J.
机构
[1] CALTECH, Div Chem & Chem Engn, Pasadena, CA 91125 USA
[2] Univ Calif Los Angeles, Calif NanoSyst Inst, Los Angeles, CA 90095 USA
[3] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
关键词
click chemistry; cycloaddition; host-guest systems; interlocked compounds; rotaxanes;
D O I
10.1002/asia.200700035
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A series of donor-acceptor [2]-, [3]-, and [4]rotaxanes and self-complexes ([1]rotaxanes) have been synthesized by a threading-followedby-stoppering approach, in which the precursor pseudorotaxanes are fixed by using Cu-I-catalyzed Huisgen 1,3-dipolar cycloaddition to attach the required stoppers. This alternative approach to forming rotaxanes of the donor-acceptor type, in which the donor is a 1,5-di-oxynaphthalene unit and the acceptor is the tetracationic cyclophane cyclobis(paraquat-p-phenylene), proceeds with enhanced yields relative to the tried and tested synthetic strategies, which involve the clipping of the cyclophane around a preformed dumbbell containing n-electron-donating recognition sites. The new synthetic approach is amenable to application to highly convergent sequences. To extend the scope of this reaction, we constructed [2]rotaxanes in which one of the phenylene rings of the tetracationic cyclophane is perfluorinated, a feature which significantly weakens its association with pi-electron-rich guests. The activation barrier for the shuttling of the cyclophane over a spacer containing two triazole rings was determined to be (15.5 +/- 0.1) kcal mol(-1) for a degenerate two-station [2]rotaxane, a value similar to that previously measured for analogous degenerate compounds containing aromatic or ethylene glycol spacers. The triazole rings do not seem to perturb the shuttling process significantly; this property bodes well for their future incorporation into bistable molecular switches.
引用
收藏
页码:634 / 647
页数:14
相关论文
共 156 条
[21]  
BASTIDE J, 1973, B SOC CHIM FR II-CH, P2871
[22]  
BASTIDE J, 1973, B SOC CHIM FR II-CH, P2555
[23]   Spiers Memorial Lecture - Molecular mechanics and molecular electronics [J].
Beckman, R ;
Beverly, K ;
Boukai, A ;
Bunimovich, Y ;
Choi, JW ;
DeIonno, E ;
Green, J ;
Johnston-Halperin, E ;
Luo, Y ;
Sheriff, B ;
Stoddart, JF ;
Heath, JR .
FARADAY DISCUSSIONS, 2006, 131 :9-22
[24]   A CHEMICALLY AND ELECTROCHEMICALLY SWITCHABLE MOLECULAR SHUTTLE [J].
BISSELL, RA ;
CORDOVA, E ;
KAIFER, AE ;
STODDART, JF .
NATURE, 1994, 369 (6476) :133-137
[25]   Titration microcalorimetry [J].
Blandamer, MJ ;
Cullis, PM ;
Engberts, JBFN .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1998, 94 (16) :2261-2267
[26]  
*BRUK AXS INC, 2002, SAINT PC VERS 6 36
[27]   Nanoscale borromean rings [J].
Cantrill, SJ ;
Chichak, KS ;
Peters, AJ ;
Stoddart, JF .
ACCOUNTS OF CHEMICAL RESEARCH, 2005, 38 (01) :1-9
[28]   Molecular composite knots [J].
Carina, RF ;
DietrichBuchecker, C ;
Sauvage, JP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (38) :9110-9116
[29]   Modular synthesis of π-acceptor cyclophanes derived from 1,4,5,8-naphthalenetetracarboxylic diimide and 1,5-dinitronaphthalene [J].
Chen, GY ;
Lean, JT ;
Alcalá, M ;
Mallouk, TE .
JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (09) :3027-3034
[30]   Dynamic nanoscale Borromean links [J].
Chichak, KS ;
Cantrill, SJ ;
Stoddart, JF .
CHEMICAL COMMUNICATIONS, 2005, (27) :3391-3393