Spatial confinement alters the ultrafast photoisomerization dynamics of azobenzenes

Otolski, Christopher J.; Raj, A. Mohan; Ramamurthy, Vaidhyanathan; Elles, Christopher G.

doi:10.1039/D0SC03955A

Title: Spatial confinement alters the ultrafast photoisomerization dynamics of azobenzenes

Journal Article · Wed Sep 16 00:00:00 EDT 2020 · Chemical Science

DOI:https://doi.org/10.1039/D0SC03955A· OSTI ID:1650211

Otolski, Christopher J. ^[1];

^[2];

^[1]

Department of Chemistry, University of Kansas, Lawrence, USA
Department of Chemistry, University of Miami, Coral Gables, USA

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.

View Journal Article

Cite

Export

Save

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; CHE-1151555; CHE-1807729

OSTI ID:: 1650211

Alternate ID(s):: OSTI ID: 1813043

Journal Information:: Chemical Science, Journal Name: Chemical Science Vol. 11 Journal Issue: 35; ISSN 2041-6520

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

References (57)

Further evidence for rotation in the π,π* and inversion in the n,π* photoisomerization of azobenzenes Rau, Hermann Journal of Photochemistry, Vol. 26, Issue 2-3 https://doi.org/10.1016/0047-2670(84)80041-6	journal	August 1984
Supramolecular control during triplet sensitized geometric isomerization of stilbenes encapsulated in a water soluble organic capsule Samanta, S. R.; Parthasarathy, A.; Ramamurthy, V. Photochemical & Photobiological Sciences, Vol. 11, Issue 11 https://doi.org/10.1039/c2pp25115a	journal	January 2012
Zinc-supported azobenzene derivative-based colorimetric fluorescent ‘turn-on’ sensing of bovine serum albumin Wang, Jing; Liu, Hai-Bo; Ha, Chang-Sik Tetrahedron, Vol. 65, Issue 47 https://doi.org/10.1016/j.tet.2009.09.102	journal	November 2009
Femtosecond Time-Resolved Fluorescence Study of Photoisomerization of trans -Azobenzene Fujino, Tatsuya; Arzhantsev, Sergei Yu.; Tahara, Tahei The Journal of Physical Chemistry A, Vol. 105, Issue 35 https://doi.org/10.1021/jp0110713	journal	September 2001
Ultrafast Dynamics of Encapsulated Molecules Reveals New Insight on the Photoisomerization Mechanism for Azobenzenes Otolski, Christopher J.; Raj, A. Mohan; Ramamurthy, Vaidhyanathan The Journal of Physical Chemistry Letters, Vol. 10, Issue 1 https://doi.org/10.1021/acs.jpclett.8b03070	journal	December 2018
Cis−Trans Isomerization of Organic Molecules and Biomolecules: Implications and Applications ^† Dugave, Christophe; Demange, Luc Chemical Reviews, Vol. 103, Issue 7 https://doi.org/10.1021/cr0104375	journal	July 2003
Picosecond Time-Resolved Raman Study of trans -Azobenzene Fujino, Tatsuya; Tahara, Tahei The Journal of Physical Chemistry A, Vol. 104, Issue 18 https://doi.org/10.1021/jp992757m	journal	May 2000
UV-Light-Induced Vibrational Coherences: The Key to Understand Kasha Rule Violation in trans -Azobenzene Nenov, Artur; Borrego-Varillas, Rocio; Oriana, Aurelio The Journal of Physical Chemistry Letters, Vol. 9, Issue 7 https://doi.org/10.1021/acs.jpclett.8b00152	journal	March 2018
Can Diarylethene Photochromism Be Explained by a Reaction Path Alone? A CASSCF Study with Model MMVB Dynamics Boggio-Pasqua, Martial; Ravaglia, Marcella; Bearpark, Michael J. The Journal of Physical Chemistry A, Vol. 107, Issue 50 https://doi.org/10.1021/jp036862e	journal	December 2003
The influence of a single thiol group on the electronic and optical properties of the smallest diamondoid adamantane Landt, Lasse; Staiger, Matthias; Wolter, David The Journal of Chemical Physics, Vol. 132, Issue 2 https://doi.org/10.1063/1.3280388	journal	January 2010
Photochemistry and Photophysics at Extended Seams of Conical Intersection Blancafort, Lluís ChemPhysChem, Vol. 15, Issue 15 https://doi.org/10.1002/cphc.201402359	journal	August 2014
Volume Conserving Geometric Isomerization of Encapsulated Azobenzenes in Ground and Excited States and as Radical Ion Mohan Raj, A.; Ramamurthy, V. Organic Letters, Vol. 19, Issue 22 https://doi.org/10.1021/acs.orglett.7b02963	journal	October 2017
Femtosecond dynamics and stimulated emission from the S2 state of a liquid crystalline trans-azobenzene Azuma, Jun; Tamai, Naoto; Shishido, Atushi Chemical Physics Letters, Vol. 288, Issue 1 https://doi.org/10.1016/S0009-2614(98)00251-6	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 Hirose, Yasushi; Yui, Hiroharu; Sawada, Tsuguo The Journal of Physical Chemistry A, Vol. 106, Issue 13 https://doi.org/10.1021/jp0138375	journal	April 2002
Femtosecond Fluorescence Dynamics of Rotation-Restricted Azobenzenophanes: New Evidence on the Mechanism of trans → cis Photoisomerization of Azobenzene Lu, Ying-Chih; Diau, Eric Wei-Guang; Rau, Hermann The Journal of Physical Chemistry A, Vol. 109, Issue 10 https://doi.org/10.1021/jp044934b	journal	March 2005
Microbial and Animal Rhodopsins: Structures, Functions, and Molecular Mechanisms Ernst, Oliver P.; Lodowski, David T.; Elstner, Marcus Chemical Reviews, Vol. 114, Issue 1 https://doi.org/10.1021/cr4003769	journal	September 2013
Contrasting the Excited-State Dynamics of the Photoactive Yellow Protein Chromophore: Protein versus Solvent Environments Vengris, Mikas; van der Horst, Michael A.; Zgrablić, Goran Biophysical Journal, Vol. 87, Issue 3 https://doi.org/10.1529/biophysj.104.043224	journal	September 2004
Photochemical reactivity of polyenes: from dienes to rhodopsin, from microseconds to femtoseconds Liu, Robert S. H.; Hammond, George S. Photochemical & Photobiological Sciences, Vol. 2, Issue 8 https://doi.org/10.1039/b304027e	journal	January 2003
Photoisomerization Dynamics of Azobenzene in Solution with S ₁ Excitation: A Femtosecond Fluorescence Anisotropy Study Chang, Chih-Wei; Lu, Ying-Chih; Wang, Tsai-Te Journal of the American Chemical Society, Vol. 126, Issue 32 https://doi.org/10.1021/ja049215p	journal	August 2004
The Quest for Photoswitches Activated by Near-Infrared Light: A Theoretical Study of the Photochemistry of BF ₂ -Coordinated Azo Derivatives Moreno, Miquel; Gelabert, Ricard; Lluch, José M. ChemPhysChem, Vol. 17, Issue 18 https://doi.org/10.1002/cphc.201600543	journal	July 2016
Femtosecond time-resolved UV-visible absorption spectroscopy of trans-azobenzene: dependence on excitation wavelength Lednev, I. K.; Ye, T. -Q.; Matousek, P. Chemical Physics Letters, Vol. 290, Issue 1-3 https://doi.org/10.1016/S0009-2614(98)00490-4	journal	June 1998
Cis-trans photoisomerization of azobenzene. Solvent and triplet donors effects Bortolus, Pietro.; Monti, Sandra. The Journal of Physical Chemistry, Vol. 83, Issue 6 https://doi.org/10.1021/j100469a002	journal	March 1979
Excited-State Dynamics of trans - and cis -Azobenzene after UV Excitation in the ππ* Band Satzger, H.; Root, C.; Braun, M. The Journal of Physical Chemistry A, Vol. 108, Issue 30 https://doi.org/10.1021/jp049509x	journal	July 2004
Breaking the Kasha Rule for More Efficient Photochemistry Demchenko, Alexander P.; Tomin, Vladimir I.; Chou, Pi-Tai Chemical Reviews, Vol. 117, Issue 21 https://doi.org/10.1021/acs.chemrev.7b00110	journal	October 2017
The effect of wavelength on organic photoreactions in solution. Reactions from upper excited states Turro, N. J.; Ramamurthy, V.; Cherry, W. Chemical Reviews, Vol. 78, Issue 2 https://doi.org/10.1021/cr60312a003	journal	April 1978
Photochemistry of azobenzene-containing polymers Kumar, G. Sudesh; Neckers, D. C. Chemical Reviews, Vol. 89, Issue 8 https://doi.org/10.1021/cr00098a012	journal	December 1989
Cycloreversion Dynamics of a Photochromic Molecular Switch via One-Photon and Sequential Two-Photon Excitation Ward, Cassandra L.; Elles, Christopher G. The Journal of Physical Chemistry A, Vol. 118, Issue 43 https://doi.org/10.1021/jp5088948	journal	October 2014
On the rotation-inversion controversy on photoisomerization of azobenzenes. Experimental proof of inversion Rau, Hermann; Lueddecke, Erik Journal of the American Chemical Society, Vol. 104, Issue 6 https://doi.org/10.1021/ja00370a028	journal	March 1982
Photoisomerization Dynamics and Pathways of trans - and cis -Azobenzene in Solution from Broadband Femtosecond Spectroscopies and Calculations Quick, M.; Dobryakov, A. L.; Gerecke, M. The Journal of Physical Chemistry B, Vol. 118, Issue 29 https://doi.org/10.1021/jp504999f	journal	July 2014
Why Does trans -Azobenzene Have a Smaller Isomerization Yield for ππ* Excitation Than for nπ* Excitation? Yuan, Shuai; Dou, Yusheng; Wu, Weifeng The Journal of Physical Chemistry A, Vol. 112, Issue 51 https://doi.org/10.1021/jp806227x	journal	December 2008
Excited-state dynamics and efficient triplet formation in phenylthiophene compounds Zheldakov, Igor L.; Wasylenko, Jenna M.; Elles, Christopher G. Physical Chemistry Chemical Physics, Vol. 14, Issue 18 https://doi.org/10.1039/c2cp23602h	journal	January 2012
Using photons to manipulate enzyme inhibition by an azobenzene-modified nucleic acid probe Kim, Y.; Phillips, J. A.; Liu, H. Proceedings of the National Academy of Sciences, Vol. 106, Issue 16 https://doi.org/10.1073/pnas.0812402106	journal	April 2009
The Different Photoisomerization Efficiency of Azobenzene in the Lowest nπ* and ππ* Singlets: The Role of a Phantom State Conti, Irene; Garavelli, Marco; Orlandi, Giorgio Journal of the American Chemical Society, Vol. 130, Issue 15 https://doi.org/10.1021/ja710275e	journal	April 2008
Well-Defined, Organic Nanoenvironments in Water: The Hydrophobic Effect Drives a Capsular Assembly Gibb, Corinne L. D.; Gibb, Bruce C. Journal of the American Chemical Society, Vol. 126, Issue 37 https://doi.org/10.1021/ja0475611	journal	September 2004
Deconvolutions based on singular value decomposition and the pseudoinverse: a guide for beginners Hendler, Richard W.; Shrager, Richard I. Journal of Biochemical and Biophysical Methods, Vol. 28, Issue 1 https://doi.org/10.1016/0165-022X(94)90061-2	journal	January 1994
Ultrafast trans → cis Photoisomerization Dynamics of Alkyl-Substituted Stilbenes in a Supramolecular Capsule Otolski, Christopher J.; Mohan Raj, A.; Sharma, Gaurav The Journal of Physical Chemistry A, Vol. 123, Issue 24 https://doi.org/10.1021/acs.jpca.9b03285	journal	May 2019
Chemistry in Restricted Spaces: Select Photodimerizations in Cages, Cavities, and Capsules Ramamurthy, V.; Parthasarathy, Anand Israel Journal of Chemistry, Vol. 51, Issue 7 https://doi.org/10.1002/ijch.201100065	journal	July 2011
A metal–organic framework as a flask: photophysics of confined chromophores with a benzylidene imidazolinone core Dolgopolova, Ekaterina A.; Moore, Thomas M.; Ejegbavwo, Otega A. Chemical Communications, Vol. 53, Issue 53 https://doi.org/10.1039/C7CC02253K	journal	January 2017
Polarization Dependence of Holographic Grating Recording in Azobenzene-Functionalized Polymers Monitored by Visible and Infrared Light Sobolewska, Anna; Bartkiewicz, Stanislaw; Miniewicz, Andrzej The Journal of Physical Chemistry B, Vol. 114, Issue 30 https://doi.org/10.1021/jp103756h	journal	August 2010
Spectroscopic Properties of Organic Azo Compounds Rau, Hermann Angewandte Chemie International Edition in English, Vol. 12, Issue 3 https://doi.org/10.1002/anie.197302241	journal	March 1973
Azobenzene photoswitches for biomolecules Beharry, Andrew A.; Woolley, G. Andrew Chemical Society Reviews, Vol. 40, Issue 8 https://doi.org/10.1039/c1cs15023e	journal	January 2011
Structural Observation of the Primary Isomerization in Vision with Femtosecond-Stimulated Raman Kukura, P. Science, Vol. 310, Issue 5750 https://doi.org/10.1126/science.1118379	journal	November 2005
Photochemistry within a Water-Soluble Organic Capsule Ramamurthy, Vaidhyanathan Accounts of Chemical Research, Vol. 48, Issue 11 https://doi.org/10.1021/acs.accounts.5b00360	journal	October 2015
Femtosecond spectroscopy reveals huge differences in the photoisomerisation dynamics between azobenzenes linked to polymers and azobenzenes in solution Bahrenburg, Julia; Renth, Falk; Temps, Friedrich Physical Chemistry Chemical Physics, Vol. 16, Issue 23 https://doi.org/10.1039/c4cp01196a	journal	January 2014
Theory and Simulation of the Ultrafast Double-Bond Isomerization of Biological Chromophores Gozem, Samer; Luk, Hoi Ling; Schapiro, Igor Chemical Reviews, Vol. 117, Issue 22 https://doi.org/10.1021/acs.chemrev.7b00177	journal	October 2017
Role of free space and weak interactions on geometric isomerization of stilbenes held in a molecular container Parthasarathy, Anand; Ramamurthy, V. Photochemical & Photobiological Sciences, Vol. 10, Issue 9 https://doi.org/10.1039/c1pp05035d	journal	January 2011
Fluorescence and Phosphorescence from Higher Excited States of Organic Molecules Itoh, Takao Chemical Reviews, Vol. 112, Issue 8 https://doi.org/10.1021/cr200166m	journal	May 2012
Femtosecond photoisomerization of cis-azobenzene Nägele, T.; Hoche, R.; Zinth, W. Chemical Physics Letters, Vol. 272, Issue 5-6 https://doi.org/10.1016/S0009-2614(97)00531-9	journal	July 1997
Multidimensional Potential Energy Surfaces Resolved at the RASPT2 Level for Accurate Photoinduced Isomerization Dynamics of Azobenzene Aleotti, Flavia; Soprani, Lorenzo; Nenov, Artur Journal of Chemical Theory and Computation, Vol. 15, Issue 12 https://doi.org/10.1021/acs.jctc.9b00561	journal	October 2019
Femtosecond Time-Resolved UV−Visible Absorption Spectroscopy of trans -Azobenzene in Solution Lednev, Igor K.; Ye, Tian-Qing; Hester, Ronald E. The Journal of Physical Chemistry, Vol. 100, Issue 32 https://doi.org/10.1021/jp9610067	journal	January 1996
Controlling Photochemical Geometric Isomerization of a Stilbene and Dimerization of a Styrene Using a Confined Reaction Cavity in Water Parthasarathy, Anand; Kaanumalle, Lakshmi S.; Ramamurthy, V. Organic Letters, Vol. 9, Issue 24 https://doi.org/10.1021/ol702322u	journal	November 2007
Light-Driven Molecular Hinge: A New Molecular Machine Showing a Light-Intensity-Dependent Photoresponse that Utilizes the Trans−Cis Isomerization of Azobenzene Norikane, Yasuo; Tamaoki, Nobuyuki Organic Letters, Vol. 6, Issue 15 https://doi.org/10.1021/ol049082c	journal	July 2004
Two-Photon Excitation of trans -Stilbene: Spectroscopy and Dynamics of Electronically Excited States above S ₁ Houk, Amanda L.; Zheldakov, Igor L.; Tommey, Tyler A. The Journal of Physical Chemistry B, Vol. 119, Issue 29 https://doi.org/10.1021/jp509959n	journal	September 2014
A New Trans-to-Cis Photoisomerization Mechanism of Azobenzene on the S ₁ (n,π*) Surface Wei-Guang Diau, Eric The Journal of Physical Chemistry A, Vol. 108, Issue 6 https://doi.org/10.1021/jp031149a	journal	February 2004
Excited-State Structure and Dynamics of cis - and trans -Azobenzene from Resonance Raman Intensity Analysis Stuart, Christina M.; Frontiera, Renee R.; Mathies, Richard A. The Journal of Physical Chemistry A, Vol. 111, Issue 48 https://doi.org/10.1021/jp0751460	journal	December 2007
Global and target analysis of time-resolved spectra van Stokkum, Ivo H. M.; Larsen, Delmar S.; van Grondelle, Rienk Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1657, Issue 2-3 https://doi.org/10.1016/j.bbabio.2004.04.011	journal	July 2004
Conical intersection dynamics of the primary photoisomerization event in vision Polli, Dario; Altoè, Piero; Weingart, Oliver Nature, Vol. 467, Issue 7314 https://doi.org/10.1038/nature09346	journal	September 2010

Similar Records

Nonadiabatic Dynamics Simulation of the Wavelength-Dependent Photochemistry of Azobenzene Excited to the nπ* and ππ* Excited States

Journal Article · Mon Nov 23 00:00:00 EST 2020 · Journal of the American Chemical Society · OSTI ID:1650211

Yu, Jimmy K.; Bannwarth, Christoph; Liang, Ruibin; +2 more

Nonadiabatic simulation study of photoisomerization of azobenzene: Detailed mechanism and load-resisting capacity

Journal Article · Tue Oct 28 00:00:00 EDT 2008 · Journal of Chemical Physics · OSTI ID:1650211

Junfeng, Shao; Yibo, Lei; Zhenyi, Wen; +2 more

Reversible work function changes induced by photoisomerization of asymmetric azobenzene dithiol self-assembled monolayers on gold

Journal Article · Mon Aug 25 00:00:00 EDT 2008 · Applied Physics Letters · OSTI ID:1650211

Wee, Andrew T. S.; Akiyama, H; Nagahiro, T; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Spatial confinement alters the ultrafast photoisomerization dynamics of azobenzenes

Citation Formats

References (57)

Similar Records

Related Subjects