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Mechanism of Oxidative Shuttling for [2]Rotaxane in a Stoddart−Heath Molecular Switch: Density Functional Theory Study with Continuum-Solvation Model

Jang, Yun Hee and Goddard, William A., III (2006) Mechanism of Oxidative Shuttling for [2]Rotaxane in a Stoddart−Heath Molecular Switch: Density Functional Theory Study with Continuum-Solvation Model. Journal of Physical Chemistry B, 110 (15). pp. 7660-7665. ISSN 1520-6106. https://resolver.caltech.edu/CaltechAUTHORS:20170606-101751463

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Abstract

The central component of the programmable molecular switch demonstrated recently by Stoddart and Heath is [2]rotaxane, which consists of a cyclobis-(paraquat-p-phenylene) ring-shaped shuttle [(CBPQT^(4+))(PF_6^-)_4] encircling a finger and moving between two stations on the finger:  tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP). We report here a quantum mechanics (QM) study of the mechanism by which movement of the ring (and in turn the on−off switching) is controlled by the oxidation−reduction process. We use B3LYP density functional theory to describe how oxidation of the [2]rotaxane components (in using Poisson−Boltzmann continuum-solvation theory for acetonitrile solution) induces the motions associated with switching (translation of the ring). These calculations support the proposal that oxidation occurs on TTF, leading to repulsion between two positive charge centers (TTF^(2+) and CBPQT^(4+)) that drives the CBPQT^(4+) ring from the TTF^(2+) station toward the neutral DNP station. The theory also supports the experimental observation that the first and second oxidation potentials are nearly the same (separated by 0.09 eV in the QM). This excellent agreement between the QM and experiment suggests that QM can be useful in designing new systems.


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http://dx.doi.org/10.1021/jp055473cDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp055473cPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jp055473cPublisherSupporting Information
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2006 American Chemical Society. Received 26 September 2005. Published online 28 March 2006. Published in print 1 April 2006. We thank Dr. Seung Soon Jang, Dr. Yong-Hoon Kim, the Prof. J. Fraser Stoddart group at UCLA, and the Prof. James Heath group of Caltech for helpful discussions. This work was initiated with support by the National Science Foundation [NIRT] and continued with support from MARCO-FENA. In addition, the facilities of the MSC were supported by ONR-DURIP, ARO-DURIP, and NSF-MRI.
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Funding AgencyGrant Number
NSFUNSPECIFIED
Microelectronics Advanced Research Corporation (MARCO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Center on Functional Engineered NanoArchitectonics (FENA)UNSPECIFIED
Issue or Number:15
Record Number:CaltechAUTHORS:20170606-101751463
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170606-101751463
Official Citation:Mechanism of Oxidative Shuttling for [2]Rotaxane in a Stoddart−Heath Molecular Switch:  Density Functional Theory Study with Continuum-Solvation Model Yun Hee Jang and William A. Goddard, III The Journal of Physical Chemistry B 2006 110 (15), 7660-7665 DOI: 10.1021/jp055473c
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77964
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:06 Jun 2017 17:42
Last Modified:03 Oct 2019 18:03

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