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Title: Spatial confinement alters the ultrafast photoisomerization dynamics of azobenzenes

Abstract

Ultrafast transient absorption spectroscopy reveals new excited-state dynamics following excitation of trans-azobenzene (t-Az) and several alkyl-substituted t-Az derivatives encapsulated in a water-soluble supramolecular host–guest complex. Encapsulation increases the excited-state lifetimes and alters the yields of the trans / cis photoisomerization reaction compared with solution. Kinetic modeling of the transient spectra for unsubstituted t-Az following nπ* and ππ* excitation reveals steric trapping of excited-state species, as well as an adiabatic excited-state trans / cis isomerization pathway for confined molecules that is not observed in solution. Analysis of the transient spectra following ππ* excitation for a series of 4-alkyl and 4,40-dialkyl substituted t-Az molecules suggests that additional crowding due to lengthening of the alkyl tails results in deeper trapping of the excited-state species, including distorted trans and cis structures. The variation of the dynamics due to crowding in the confined environment provides new evidence to explain the violation of Kasha's rule for nπ* and ππ* excitation of azobenzenes based on competition between in-plane inversion and out-of-plane rotation channels.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Department of Chemistry, University of Kansas, Lawrence, USA
  2. Department of Chemistry, University of Miami, Coral Gables, USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1650211
Alternate Identifier(s):
OSTI ID: 1813043
Grant/Contract Number:  
AC02-06CH11357; CHE-1151555; CHE-1807729
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 35; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Otolski, Christopher J., Raj, A. Mohan, Ramamurthy, Vaidhyanathan, and Elles, Christopher G. Spatial confinement alters the ultrafast photoisomerization dynamics of azobenzenes. United Kingdom: N. p., 2020. Web. doi:10.1039/D0SC03955A.
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Otolski, Christopher J., Raj, A. Mohan, Ramamurthy, Vaidhyanathan, & Elles, Christopher G. Spatial confinement alters the ultrafast photoisomerization dynamics of azobenzenes. United Kingdom. https://doi.org/10.1039/D0SC03955A
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Otolski, Christopher J., Raj, A. Mohan, Ramamurthy, Vaidhyanathan, and Elles, Christopher G. Wed . "Spatial confinement alters the ultrafast photoisomerization dynamics of azobenzenes". United Kingdom. https://doi.org/10.1039/D0SC03955A.
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@article{osti_1650211,
title = {Spatial confinement alters the ultrafast photoisomerization dynamics of azobenzenes},
author = {Otolski, Christopher J. and Raj, A. Mohan and Ramamurthy, Vaidhyanathan and Elles, Christopher G.},
abstractNote = {Ultrafast transient absorption spectroscopy reveals new excited-state dynamics following excitation of trans-azobenzene (t-Az) and several alkyl-substituted t-Az derivatives encapsulated in a water-soluble supramolecular host–guest complex. Encapsulation increases the excited-state lifetimes and alters the yields of the trans / cis photoisomerization reaction compared with solution. Kinetic modeling of the transient spectra for unsubstituted t-Az following nπ* and ππ* excitation reveals steric trapping of excited-state species, as well as an adiabatic excited-state trans / cis isomerization pathway for confined molecules that is not observed in solution. Analysis of the transient spectra following ππ* excitation for a series of 4-alkyl and 4,40-dialkyl substituted t-Az molecules suggests that additional crowding due to lengthening of the alkyl tails results in deeper trapping of the excited-state species, including distorted trans and cis structures. The variation of the dynamics due to crowding in the confined environment provides new evidence to explain the violation of Kasha's rule for nπ* and ππ* excitation of azobenzenes based on competition between in-plane inversion and out-of-plane rotation channels.},
doi = {10.1039/D0SC03955A},
journal = {Chemical Science},
number = 35,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {9}
}
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https://doi.org/10.1039/D0SC03955A
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