skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry, University of Kansas, Lawrence, USA
  2. Department of Chemistry, University of Miami, Coral Gables, USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1650211
Grant/Contract Number:  
AC02-06CH11357
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

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. https://doi.org/10.1039/D0SC03955A.
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
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.
@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.},
doi = {10.1039/D0SC03955A},
journal = {Chemical Science},
number = 35,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/D0SC03955A

Save / Share:

Works referenced in this record:

Further evidence for rotation in the π,π* and inversion in the n,π* photoisomerization of azobenzenes
journal, August 1984


Supramolecular control during triplet sensitized geometric isomerization of stilbenes encapsulated in a water soluble organic capsule
journal, January 2012

  • Samanta, S. R.; Parthasarathy, A.; Ramamurthy, V.
  • Photochemical & Photobiological Sciences, Vol. 11, Issue 11
  • DOI: 10.1039/c2pp25115a

Zinc-supported azobenzene derivative-based colorimetric fluorescent ‘turn-on’ sensing of bovine serum albumin
journal, November 2009


Femtosecond Time-Resolved Fluorescence Study of Photoisomerization of trans -Azobenzene
journal, September 2001

  • Fujino, Tatsuya; Arzhantsev, Sergei Yu.; Tahara, Tahei
  • The Journal of Physical Chemistry A, Vol. 105, Issue 35
  • DOI: 10.1021/jp0110713

Ultrafast Dynamics of Encapsulated Molecules Reveals New Insight on the Photoisomerization Mechanism for Azobenzenes
journal, December 2018

  • Otolski, Christopher J.; Raj, A. Mohan; Ramamurthy, Vaidhyanathan
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 1
  • DOI: 10.1021/acs.jpclett.8b03070

Cis−Trans Isomerization of Organic Molecules and Biomolecules:  Implications and Applications
journal, July 2003

  • Dugave, Christophe; Demange, Luc
  • Chemical Reviews, Vol. 103, Issue 7
  • DOI: 10.1021/cr0104375

Picosecond Time-Resolved Raman Study of trans -Azobenzene
journal, May 2000

  • Fujino, Tatsuya; Tahara, Tahei
  • The Journal of Physical Chemistry A, Vol. 104, Issue 18
  • DOI: 10.1021/jp992757m

UV-Light-Induced Vibrational Coherences: The Key to Understand Kasha Rule Violation in trans -Azobenzene
journal, March 2018

  • Nenov, Artur; Borrego-Varillas, Rocio; Oriana, Aurelio
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 7
  • DOI: 10.1021/acs.jpclett.8b00152

Can Diarylethene Photochromism Be Explained by a Reaction Path Alone? A CASSCF Study with Model MMVB Dynamics
journal, December 2003

  • Boggio-Pasqua, Martial; Ravaglia, Marcella; Bearpark, Michael J.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 50
  • DOI: 10.1021/jp036862e

The influence of a single thiol group on the electronic and optical properties of the smallest diamondoid adamantane
journal, January 2010

  • Landt, Lasse; Staiger, Matthias; Wolter, David
  • The Journal of Chemical Physics, Vol. 132, Issue 2
  • DOI: 10.1063/1.3280388

Photochemistry and Photophysics at Extended Seams of Conical Intersection
journal, August 2014


Volume Conserving Geometric Isomerization of Encapsulated Azobenzenes in Ground and Excited States and as Radical Ion
journal, October 2017


Femtosecond dynamics and stimulated emission from the S2 state of a liquid crystalline trans-azobenzene
journal, May 1998


Effect of Potential Energy Gap between the n-π* and the π-π* State on Ultrafast Photoisomerization Dynamics of an Azobenzene Derivative
journal, April 2002

  • Hirose, Yasushi; Yui, Hiroharu; Sawada, Tsuguo
  • The Journal of Physical Chemistry A, Vol. 106, Issue 13
  • DOI: 10.1021/jp0138375

Femtosecond Fluorescence Dynamics of Rotation-Restricted Azobenzenophanes:  New Evidence on the Mechanism of transcis Photoisomerization of Azobenzene
journal, March 2005

  • Lu, Ying-Chih; Diau, Eric Wei-Guang; Rau, Hermann
  • The Journal of Physical Chemistry A, Vol. 109, Issue 10
  • DOI: 10.1021/jp044934b

Microbial and Animal Rhodopsins: Structures, Functions, and Molecular Mechanisms
journal, September 2013

  • Ernst, Oliver P.; Lodowski, David T.; Elstner, Marcus
  • Chemical Reviews, Vol. 114, Issue 1
  • DOI: 10.1021/cr4003769

Contrasting the Excited-State Dynamics of the Photoactive Yellow Protein Chromophore: Protein versus Solvent Environments
journal, September 2004


Photochemical reactivity of polyenes: from dienes to rhodopsin, from microseconds to femtoseconds
journal, January 2003

  • Liu, Robert S. H.; Hammond, George S.
  • Photochemical & Photobiological Sciences, Vol. 2, Issue 8
  • DOI: 10.1039/b304027e

Photoisomerization Dynamics of Azobenzene in Solution with S 1 Excitation:  A Femtosecond Fluorescence Anisotropy Study
journal, August 2004

  • Chang, Chih-Wei; Lu, Ying-Chih; Wang, Tsai-Te
  • Journal of the American Chemical Society, Vol. 126, Issue 32
  • DOI: 10.1021/ja049215p

The Quest for Photoswitches Activated by Near-Infrared Light: A Theoretical Study of the Photochemistry of BF 2 -Coordinated Azo Derivatives
journal, July 2016

  • Moreno, Miquel; Gelabert, Ricard; Lluch, José M.
  • ChemPhysChem, Vol. 17, Issue 18
  • DOI: 10.1002/cphc.201600543

Femtosecond time-resolved UV-visible absorption spectroscopy of trans-azobenzene: dependence on excitation wavelength
journal, June 1998


Cis-trans photoisomerization of azobenzene. Solvent and triplet donors effects
journal, March 1979

  • Bortolus, Pietro.; Monti, Sandra.
  • The Journal of Physical Chemistry, Vol. 83, Issue 6
  • DOI: 10.1021/j100469a002

Excited-State Dynamics of trans - and cis -Azobenzene after UV Excitation in the ππ* Band
journal, July 2004

  • Satzger, H.; Root, C.; Braun, M.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 30
  • DOI: 10.1021/jp049509x

Breaking the Kasha Rule for More Efficient Photochemistry
journal, October 2017


The effect of wavelength on organic photoreactions in solution. Reactions from upper excited states
journal, April 1978

  • Turro, N. J.; Ramamurthy, V.; Cherry, W.
  • Chemical Reviews, Vol. 78, Issue 2
  • DOI: 10.1021/cr60312a003

Photochemistry of azobenzene-containing polymers
journal, December 1989


Cycloreversion Dynamics of a Photochromic Molecular Switch via One-Photon and Sequential Two-Photon Excitation
journal, October 2014

  • Ward, Cassandra L.; Elles, Christopher G.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 43
  • DOI: 10.1021/jp5088948

On the rotation-inversion controversy on photoisomerization of azobenzenes. Experimental proof of inversion
journal, March 1982

  • Rau, Hermann; Lueddecke, Erik
  • Journal of the American Chemical Society, Vol. 104, Issue 6
  • DOI: 10.1021/ja00370a028

Photoisomerization Dynamics and Pathways of trans - and cis -Azobenzene in Solution from Broadband Femtosecond Spectroscopies and Calculations
journal, July 2014

  • Quick, M.; Dobryakov, A. L.; Gerecke, M.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 29
  • DOI: 10.1021/jp504999f

Why Does trans -Azobenzene Have a Smaller Isomerization Yield for ππ* Excitation Than for nπ* Excitation?
journal, December 2008

  • Yuan, Shuai; Dou, Yusheng; Wu, Weifeng
  • The Journal of Physical Chemistry A, Vol. 112, Issue 51
  • DOI: 10.1021/jp806227x

Excited-state dynamics and efficient triplet formation in phenylthiophene compounds
journal, January 2012

  • Zheldakov, Igor L.; Wasylenko, Jenna M.; Elles, Christopher G.
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 18
  • DOI: 10.1039/c2cp23602h

Using photons to manipulate enzyme inhibition by an azobenzene-modified nucleic acid probe
journal, April 2009

  • Kim, Y.; Phillips, J. A.; Liu, H.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 16
  • DOI: 10.1073/pnas.0812402106

The Different Photoisomerization Efficiency of Azobenzene in the Lowest nπ* and ππ* Singlets: The Role of a Phantom State
journal, April 2008

  • Conti, Irene; Garavelli, Marco; Orlandi, Giorgio
  • Journal of the American Chemical Society, Vol. 130, Issue 15
  • DOI: 10.1021/ja710275e

Well-Defined, Organic Nanoenvironments in Water:  The Hydrophobic Effect Drives a Capsular Assembly
journal, September 2004

  • Gibb, Corinne L. D.; Gibb, Bruce C.
  • Journal of the American Chemical Society, Vol. 126, Issue 37
  • DOI: 10.1021/ja0475611

Deconvolutions based on singular value decomposition and the pseudoinverse: a guide for beginners
journal, January 1994

  • Hendler, Richard W.; Shrager, Richard I.
  • Journal of Biochemical and Biophysical Methods, Vol. 28, Issue 1
  • DOI: 10.1016/0165-022X(94)90061-2

Ultrafast trans → cis Photoisomerization Dynamics of Alkyl-Substituted Stilbenes in a Supramolecular Capsule
journal, May 2019

  • Otolski, Christopher J.; Mohan Raj, A.; Sharma, Gaurav
  • The Journal of Physical Chemistry A, Vol. 123, Issue 24
  • DOI: 10.1021/acs.jpca.9b03285

Chemistry in Restricted Spaces: Select Photodimerizations in Cages, Cavities, and Capsules
journal, July 2011

  • Ramamurthy, V.; Parthasarathy, Anand
  • Israel Journal of Chemistry, Vol. 51, Issue 7
  • DOI: 10.1002/ijch.201100065

A metal–organic framework as a flask: photophysics of confined chromophores with a benzylidene imidazolinone core
journal, January 2017

  • Dolgopolova, Ekaterina A.; Moore, Thomas M.; Ejegbavwo, Otega A.
  • Chemical Communications, Vol. 53, Issue 53
  • DOI: 10.1039/C7CC02253K

Polarization Dependence of Holographic Grating Recording in Azobenzene-Functionalized Polymers Monitored by Visible and Infrared Light
journal, August 2010

  • Sobolewska, Anna; Bartkiewicz, Stanislaw; Miniewicz, Andrzej
  • The Journal of Physical Chemistry B, Vol. 114, Issue 30
  • DOI: 10.1021/jp103756h

Spectroscopic Properties of Organic Azo Compounds
journal, March 1973

  • Rau, Hermann
  • Angewandte Chemie International Edition in English, Vol. 12, Issue 3
  • DOI: 10.1002/anie.197302241

Azobenzene photoswitches for biomolecules
journal, January 2011

  • Beharry, Andrew A.; Woolley, G. Andrew
  • Chemical Society Reviews, Vol. 40, Issue 8
  • DOI: 10.1039/c1cs15023e

Photochemistry within a Water-Soluble Organic Capsule
journal, October 2015


Photoisomerization in different classes of azobenzene
journal, January 2012

  • Bandara, H. M. Dhammika; Burdette, Shawn C.
  • Chem. Soc. Rev., Vol. 41, Issue 5
  • DOI: 10.1039/C1CS15179G

Femtosecond spectroscopy reveals huge differences in the photoisomerisation dynamics between azobenzenes linked to polymers and azobenzenes in solution
journal, January 2014

  • Bahrenburg, Julia; Renth, Falk; Temps, Friedrich
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 23
  • DOI: 10.1039/c4cp01196a

Theory and Simulation of the Ultrafast Double-Bond Isomerization of Biological Chromophores
journal, October 2017


Role of free space and weak interactions on geometric isomerization of stilbenes held in a molecular container
journal, January 2011

  • Parthasarathy, Anand; Ramamurthy, V.
  • Photochemical & Photobiological Sciences, Vol. 10, Issue 9
  • DOI: 10.1039/c1pp05035d

Fluorescence and Phosphorescence from Higher Excited States of Organic Molecules
journal, May 2012


Femtosecond photoisomerization of cis-azobenzene
journal, July 1997


Multidimensional Potential Energy Surfaces Resolved at the RASPT2 Level for Accurate Photoinduced Isomerization Dynamics of Azobenzene
journal, October 2019

  • Aleotti, Flavia; Soprani, Lorenzo; Nenov, Artur
  • Journal of Chemical Theory and Computation, Vol. 15, Issue 12
  • DOI: 10.1021/acs.jctc.9b00561

Femtosecond Time-Resolved UV−Visible Absorption Spectroscopy of trans -Azobenzene in Solution
journal, January 1996

  • Lednev, Igor K.; Ye, Tian-Qing; Hester, Ronald E.
  • The Journal of Physical Chemistry, Vol. 100, Issue 32
  • DOI: 10.1021/jp9610067

Controlling Photochemical Geometric Isomerization of a Stilbene and Dimerization of a Styrene Using a Confined Reaction Cavity in Water
journal, November 2007

  • Parthasarathy, Anand; Kaanumalle, Lakshmi S.; Ramamurthy, V.
  • Organic Letters, Vol. 9, Issue 24
  • DOI: 10.1021/ol702322u

Two-Photon Excitation of trans -Stilbene: Spectroscopy and Dynamics of Electronically Excited States above S 1
journal, September 2014

  • Houk, Amanda L.; Zheldakov, Igor L.; Tommey, Tyler A.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 29
  • DOI: 10.1021/jp509959n

A New Trans-to-Cis Photoisomerization Mechanism of Azobenzene on the S 1 (n,π*) Surface
journal, February 2004

  • Wei-Guang Diau, Eric
  • The Journal of Physical Chemistry A, Vol. 108, Issue 6
  • DOI: 10.1021/jp031149a

Excited-State Structure and Dynamics of cis - and trans -Azobenzene from Resonance Raman Intensity Analysis
journal, December 2007

  • Stuart, Christina M.; Frontiera, Renee R.; Mathies, Richard A.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 48
  • DOI: 10.1021/jp0751460

Global and target analysis of time-resolved spectra
journal, July 2004

  • van Stokkum, Ivo H. M.; Larsen, Delmar S.; van Grondelle, Rienk
  • Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1657, Issue 2-3
  • DOI: 10.1016/j.bbabio.2004.04.011

Conical intersection dynamics of the primary photoisomerization event in vision
journal, September 2010

  • Polli, Dario; Altoè, Piero; Weingart, Oliver
  • Nature, Vol. 467, Issue 7314
  • DOI: 10.1038/nature09346