Comprehensive theoretical study of the conversion reactions of spiropyrans: Substituent and solvent effects

Yinghong Sheng, Jerzy Leszczynski, Antonio Garcia, Rohit Rosario, Devens Gust, Joseph Springer

Research output: Contribution to journalArticle

132 Citations (Scopus)

Abstract

A comprehensive theoretical study of the reaction mechanisms for the conversion between spiropyrans (SPs) and the open form of merocyanines (MCs) has been conducted by theoretical calculations. The reaction mechanisms on the ground- and triplet-state potential energy surfaces (PESs) were investigated using the density functional method. Time-dependent density functional theory (TD-DFT) calculations using the CIS optimized excited-state geometries were carried out to study the reaction mechanisms on the lowest excited singlet-state PES. Two possible reaction mechanisms for the thermal conversion between SPs to MCs were found on the ground-state PES. The geometrical parameter, BLA (Bond Length Alternation), which correlates the strengths of the substituents and the polarities of solvents, was used to explain the changes in the reaction mechanism induced by the different donor-acceptor pairs and solvents. In addition, the reaction mechanisms of spiropyran↔merocyanine conversion on the triplet and the lowest excited singlet potential energy surfaces were also studied; several possible reaction mechanisms on the excited-state PESs were proposed. A comprehensive mechanistic view of the ultrafast photochemistry of spiropyrans was revealed and interpreted in terms of the strengths of substituents and the polarity of solvents.

Original languageEnglish (US)
Pages (from-to)16233-16243
Number of pages11
JournalJournal of Physical Chemistry B
Volume108
Issue number41
DOIs
StatePublished - Oct 14 2004

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Potential energy surfaces
Excited states
potential energy
polarity
Photochemical reactions
Bond length
excitation
Ground state
Density functional theory
Commonwealth of Independent States
ground state
alternations
spiropyran
photochemical reactions
atomic energy levels
Geometry
density functional theory
geometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Comprehensive theoretical study of the conversion reactions of spiropyrans : Substituent and solvent effects. / Sheng, Yinghong; Leszczynski, Jerzy; Garcia, Antonio; Rosario, Rohit; Gust, Devens; Springer, Joseph.

In: Journal of Physical Chemistry B, Vol. 108, No. 41, 14.10.2004, p. 16233-16243.

Research output: Contribution to journalArticle

Sheng, Y, Leszczynski, J, Garcia, A, Rosario, R, Gust, D & Springer, J 2004, 'Comprehensive theoretical study of the conversion reactions of spiropyrans: Substituent and solvent effects', Journal of Physical Chemistry B, vol. 108, no. 41, pp. 16233-16243. https://doi.org/10.1021/jp0488867
Sheng, Yinghong ; Leszczynski, Jerzy ; Garcia, Antonio ; Rosario, Rohit ; Gust, Devens ; Springer, Joseph. / Comprehensive theoretical study of the conversion reactions of spiropyrans : Substituent and solvent effects. In: Journal of Physical Chemistry B. 2004 ; Vol. 108, No. 41. pp. 16233-16243.
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