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Ground‐State Equilibrium Thermodynamics and Switching Kinetics of Bistable [2]Rotaxanes Switched in Solution, Polymer Gels, and Molecular Electronic Devices
Author(s) -
Choi Jang Wook,
Flood Amar H.,
Steuerman David W.,
Nygaard Sune,
Braunschweig Adam B.,
Moonen Nicolle N. P.,
Laursen Bo W.,
Luo Yi,
DeIonno Erica,
Peters Andrea J.,
Jeppesen Jan O.,
Xu Ke,
Stoddart J. Fraser,
Heath James R.
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200500934
Subject(s) - rotaxane , chemistry , bistability , acetonitrile , tetrathiafulvalene , polymer , kinetics , ring (chemistry) , electrolyte , relaxation (psychology) , thermodynamics , crystallography , polymer chemistry , molecule , supramolecular chemistry , materials science , crystal structure , organic chemistry , electrode , physics , optoelectronics , quantum mechanics , psychology , social psychology
Abstract We report on the kinetics and ground‐state thermodynamics associated with electrochemically driven molecular mechanical switching of three bistable [2]rotaxanes in acetonitrile solution, polymer electrolyte gels, and molecular‐switch tunnel junctions (MSTJs). For all rotaxanes a π‐electron‐deficient cyclobis(paraquat‐ p ‐phenylene) (CBPQT 4+ ) ring component encircles one of two recognition sites within a dumbbell component. Two rotaxanes (RATTF 4+ and RTTF 4+ ) contain tetrathiafulvalene (TTF) and 1,5‐dioxynaphthalene (DNP) recognition units, but different hydrophilic stoppers. For these rotaxanes, the CBPQT 4+ ring encircles predominantly (>90 %) the TTF unit at equilibrium, and this equilibrium is relatively temperature independent. In the third rotaxane (RBPTTF 4+ ), the TTF unit is replaced by a π‐extended analogue (a bispyrrolotetrathiafulvalene (BPTTF) unit), and the CBPQT 4+ ring encircles almost equally both recognition sites at equilibrium. This equilibrium exhibits strong temperature dependence. These thermodynamic differences were rationalized by reference to binding constants obtained by isothermal titration calorimetry for the complexation of model guests by the CBPQT 4+ host in acetonitrile. For all bistable rotaxanes, oxidation of the TTF (BPTTF) unit is accompanied by movement of the CBPQT 4+ ring to the DNP site. Reduction back to TTF 0 (BPTTF 0 ) is followed by relaxation to the equilibrium distribution of translational isomers. The relaxation kinetics are strongly environmentally dependent, yet consistent with a single electromechanical‐switching mechanism in acetonitrile, polymer electrolyte gels, and MSTJs. The ground‐state equilibrium properties of all three bistable [2]rotaxanes were reflective of molecular structure in all environments. These results provide direct evidence for the control by molecular structure of the electronic properties exhibited by the MSTJs.