Kinetic versus thermodynamic control during the formation of [2]rotaxanes by a dynamic template-directed clipping process

被引:84
作者
Horn, M [1 ]
Ihringer, J [1 ]
Glink, PT [1 ]
Stoddart, JF [1 ]
机构
[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
关键词
crown compounds; dynamic covalent chemistry; rotaxanes; self-assembly; supramolecular chemistry;
D O I
10.1002/chem.200204479
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A template-directed dynamic clipping procedure has generated a library of nine [2]rotaxanes that have been formed from three dialkylammonium salts-acting as the dumbbell-shaped components-and three dynamic, imino bond-containing, [24]crown-8-like macrocycles-acting as the ring-shaped components-which are themselves assembled from three dialdehydes and one diamine. The rates of formation of these [2]rotaxanes differ dramatically, from minutes to days depending on the choice of dialkylammonium ion and dialdehyde, as do their thermodynamic stabilities. Generally, [2]rotaxanes formed by using 2,6-diformylpyridine as the dialdehyde component, or bis(3,5-bis(trifluoromethyl)benzyl)ammonium hexafluorophosphate as the dumbbell-shaped component, assembled the most rapidly. Those rotaxanes containing this particular electron-deficient dumbbell-shaped unit, or 2,5-diformylfuran units in the macroring, were the most stable thermodynamically. The relative thermodynamic stabilities of all nine of the [2]rotaxanes were determined by competition experiments that were monitored by H-1 NMR spectroscopy.
引用
收藏
页码:4046 / 4054
页数:9
相关论文
共 141 条
[1]  
Amirsakis DG, 2001, ANGEW CHEM INT EDIT, V40, P4256, DOI 10.1002/1521-3773(20011119)40:22<4256::AID-ANIE4256>3.0.CO
[2]  
2-S
[3]   EXPANDING ROLES FOR TEMPLATES IN SYNTHESIS [J].
ANDERSON, S ;
ANDERSON, HL ;
SANDERS, JKM .
ACCOUNTS OF CHEMICAL RESEARCH, 1993, 26 (09) :469-475
[4]   Long-range electron transfer in porphyrin-containing [2]-rotaxanes:: Tuning the rate by metal cation coordination [J].
Andersson, M ;
Linke, M ;
Chambron, JC ;
Davidsson, J ;
Heitz, V ;
Hammarström, L ;
Sauvage, JP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (16) :4347-4362
[5]  
[Anonymous], 2002, ANGEW CHEM, DOI DOI 10.1002/1521-3757(20020802)114:153.0.CO
[6]  
2-8
[7]   Spectroscopic and crystallographic studies on the stability of self-assembled coordination nanotubes [J].
Aoyagi, M ;
Tashiro, S ;
Tominaga, M ;
Biradha, K ;
Fujita, M .
CHEMICAL COMMUNICATIONS, 2002, (18) :2036-2037
[8]   Preparation of porphyrin-stoppered rotaxane aiming at immobilization on substrate [J].
Asakawa, M ;
Ikeda, T ;
Yui, N ;
Shimizu, T .
CHEMISTRY LETTERS, 2002, (02) :174-175
[9]   Switching "on" and "off" the expression of chirality in peptide rotaxanes [J].
Asakawa, M ;
Brancato, G ;
Fanti, M ;
Leigh, DA ;
Shimizu, T ;
Slawin, AMZ ;
Wong, JKY ;
Zerbetto, F ;
Zhang, SW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (12) :2939-2950
[10]   Tetrathiafulvalene-containing pseudorotaxanes formed between dibenzylammonium salts and crown ethers [J].
Ashton, PR ;
Becher, J ;
Fyfe, MCT ;
Nielsen, MB ;
Stoddart, JF ;
White, AJP ;
Williams, DJ .
TETRAHEDRON, 2001, 57 (06) :947-956