Thermodynamic forecasting of mechanically interlocked switches

Mark A. Olson, Adam Braunschweig, Taichi Ikeda, Lei Fang, Ali Trabolsi, Alexandra M Z Slawin, Saeed I. Khan, J. Fraser Stoddart

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

Mechanically interlocked molecular (MIM) switches in the form of bistable [2]rotaxanes and [2]catenanes have proven to be - when incorporated in molecular electronic devices (MEDs) and in nanoelectromechanical systems (NEMS) - a realistic and viable alternative to the silicon chip density challenge. Structural modifications and chemical environment can have a large impact on the relaxation thermodynamics of the molecular motions, such as translation and circumrotation in bistable rotaxanes and catenanes responsible for the operation of devices based on MIMs. The effects of structural modifications on the difference in free energy (ΔGo) for the equilibrium processes in switchable MIMs can be predicted by considering, firstly, the interactions present in their precursor pseudorotaxanes. By employing isothermal titration microcalorimetry (ITC) to investigate the thermodynamic parameters governing pseudorotaxane formation for a series of monosubstituted, acceptor host cyclophanes with various donor guests, in conjunction with X-ray crystallographic data, an obvious link between the noncovalent bonding interactions in pseudorotaxanes and MIMs that survive following the formation of the mechanical bond can be identified. It follows that the changes (ΔΔGo values) in the difference of free energy during the formation of different pseudorotaxanes can subsequently be extrapolated to predict ΔGo values for the thermodynamics associated with switching in analogous MIM switches, employing the same donor-acceptor recognition components. In this manner, a systematic and predictive thermodynamic approach to designing and tuning switchable MIMs and MIM-based materials has been established. Additionally, these thermodynamic relationships are reminiscent of the long forgotten concept of the 'parachor' as a molecular descriptor with respect to the additivity of physical properties in chemical systems dealing specifically with quantitative structure property-activity relationships (QSPR/QSAR).

Original languageEnglish (US)
Pages (from-to)4391-4405
Number of pages15
JournalOrganic and Biomolecular Chemistry
Volume7
Issue number21
DOIs
StatePublished - 2009
Externally publishedYes

Fingerprint

Rotaxanes
MIM (semiconductors)
Thermodynamics
forecasting
switches
Switches
thermodynamics
Quantitative Structure-Activity Relationship
Catenanes
Free energy
free energy
molecular electronics
NEMS
Molecular electronics
Equipment and Supplies
titration
Silicon
Titration
physical properties
Telecommunication links

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Biochemistry

Cite this

Olson, M. A., Braunschweig, A., Ikeda, T., Fang, L., Trabolsi, A., Slawin, A. M. Z., ... Stoddart, J. F. (2009). Thermodynamic forecasting of mechanically interlocked switches. Organic and Biomolecular Chemistry, 7(21), 4391-4405. https://doi.org/10.1039/b911874h

Thermodynamic forecasting of mechanically interlocked switches. / Olson, Mark A.; Braunschweig, Adam; Ikeda, Taichi; Fang, Lei; Trabolsi, Ali; Slawin, Alexandra M Z; Khan, Saeed I.; Stoddart, J. Fraser.

In: Organic and Biomolecular Chemistry, Vol. 7, No. 21, 2009, p. 4391-4405.

Research output: Contribution to journalArticle

Olson, MA, Braunschweig, A, Ikeda, T, Fang, L, Trabolsi, A, Slawin, AMZ, Khan, SI & Stoddart, JF 2009, 'Thermodynamic forecasting of mechanically interlocked switches', Organic and Biomolecular Chemistry, vol. 7, no. 21, pp. 4391-4405. https://doi.org/10.1039/b911874h
Olson MA, Braunschweig A, Ikeda T, Fang L, Trabolsi A, Slawin AMZ et al. Thermodynamic forecasting of mechanically interlocked switches. Organic and Biomolecular Chemistry. 2009;7(21):4391-4405. https://doi.org/10.1039/b911874h
Olson, Mark A. ; Braunschweig, Adam ; Ikeda, Taichi ; Fang, Lei ; Trabolsi, Ali ; Slawin, Alexandra M Z ; Khan, Saeed I. ; Stoddart, J. Fraser. / Thermodynamic forecasting of mechanically interlocked switches. In: Organic and Biomolecular Chemistry. 2009 ; Vol. 7, No. 21. pp. 4391-4405.
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