ACS Publications. Most Trusted. Most Cited. Most Read
Solvent Polarity Tunes the Barrier Height for Twisted Intramolecular Charge Transfer in N-Pyrrolobenzonitrile (PBN)
My Activity
    Article

    Solvent Polarity Tunes the Barrier Height for Twisted Intramolecular Charge Transfer in N-Pyrrolobenzonitrile (PBN)
    Click to copy article linkArticle link copied!

    View Author Information
    Interdisciplinary Center for Scientific Computing, Ruprecht-Karls University, Im Neuenheimer Feld 368, 69120 Heidelberg, Germany
    Institute of Physical and Theoretical Chemistry, Goethe-University, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany
    *(M.V.B.) E-mail: [email protected]
    *(A.D.) E-mail: [email protected]
    Other Access Options

    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2016, 120, 1, 14–27
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.5b09115
    Published December 6, 2015
    Copyright © 2015 American Chemical Society

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    4-(1H-pyrrol-1-yl)benzonitrile (PBN) is a typical intramolecular donor–acceptor (D/A) molecule that shows dual fluorescence in weakly polar environments. In this work the underlying photochemical reaction mechanism is investigated theoretically by using high-level ab initio methods including the recently implemented third order algebraic diagrammatic construction of the polarization propagator (ADC(3)). Solvation effects have been considered by using different sophisticated continuum model approaches. Our results conclusively explain all available experimental findings including the effects of excitation wavelength, temperature and solvent polarity. After photoexcitation in gas phase to the bright 2A (S2, ππ*) state, PBN relaxes on the 2A state surface until a conical intersection with the energetically close-lying dark 1B (S1, LE) state is reached. After passing this conical intersection PBN further relaxes on the LE state surface toward a minimum from which emission can occur. In polar environments this picture changes. Then the polar 2B (S3, CT) state is stabilized and an energy barrier along the twisting coordinate vanishes. As a consequence population of the twisted 2B state minimum becomes the dominating decay channel and red-shifted fluorescence occurs.

    Copyright © 2015 American Chemical Society

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai

    This article is cited by 16 publications.

    1. Parisa Yasini, Stuart Shepard, Manuel Smeu, Eric Borguet. Modulation of Charge Transport through Single Molecules Induced by Solvent-Stabilized Intramolecular Charge Transfer. The Journal of Physical Chemistry B 2023, 127 (45) , 9771-9780. https://doi.org/10.1021/acs.jpcb.3c03576
    2. Pierre-François Loos, Denis Jacquemin. Is ADC(3) as Accurate as CC3 for Valence and Rydberg Transition Energies?. The Journal of Physical Chemistry Letters 2020, 11 (3) , 974-980. https://doi.org/10.1021/acs.jpclett.9b03652
    3. Yang-Hui Luo, Chen Chen, Chang He, Ying-Yu Zhu, Dan-Li Hong, Xiao-Tong He, Pei-Jing An, Hong-Shuai Wu, Bai-Wang Sun. Single-Layered Two-Dimensional Metal–Organic Framework Nanosheets as an in Situ Visual Test Paper for Solvents. ACS Applied Materials & Interfaces 2018, 10 (34) , 28860-28867. https://doi.org/10.1021/acsami.8b08739
    4. Ibrahim Ahmed Z. Al-Ansari . Role of Solvent Polarity and Hydrogen-Bonding on Excited-State Fluorescence of 3-[(E)-{4-[Dimethylamino]benzylidene}amino]-2-naphthoic Acid (DMAMN): Isomerization vs Rotomerization. The Journal of Physical Chemistry A 2018, 122 (7) , 1838-1854. https://doi.org/10.1021/acs.jpca.7b11623
    5. Mercedes Vanessa Bohnwagner and Andreas Dreuw . Regular Fluorescence of 4-Fluoro-N,N-dimethylaniline: No Charge Transfer and No Twisting. The Journal of Physical Chemistry A 2017, 121 (31) , 5834-5841. https://doi.org/10.1021/acs.jpca.7b05939
    6. Matheus Máximo‐Canadas, Lucas Modesto‐Costa, Itamar Borges. Ab initio electronic absorption spectra of para ‐nitroaniline in different solvents: Intramolecular charge transfer effects. Journal of Computational Chemistry 2024, 45 (32) , 2899-2911. https://doi.org/10.1002/jcc.27493
    7. Matheus Máximo-Canadas, Itamar Borges. Absorption spectra of p–nitroaniline derivatives: charge transfer effects and the role of substituents. Journal of Molecular Modeling 2024, 30 (5) https://doi.org/10.1007/s00894-024-05917-0
    8. Cheng Chen, Chong Fang. Fluorescence Modulation by Amines: Mechanistic Insights into Twisted Intramolecular Charge Transfer (TICT) and Beyond. Chemosensors 2023, 11 (2) , 87. https://doi.org/10.3390/chemosensors11020087
    9. Neeraj Kumar Karmakar, Swati Pandey, Ravindra Kumar Pandey, Shiv Shankar Shukla. Solvatochromism: a tool for solvent discretion for UV-Vis spectroscopic studies. Applied Spectroscopy Reviews 2021, 56 (6) , 513-529. https://doi.org/10.1080/05704928.2020.1838918
    10. Huo-Lei Peng. Why does 4-biphenyl carbonyl azide have ultra-short lived excited states? An ultrafast UV-vis spectroscopic and computational study. Physical Chemistry Chemical Physics 2018, 20 (46) , 29091-29104. https://doi.org/10.1039/C8CP05963B
    11. Lucas Modesto-Costa, Itamar Borges. Discrete and continuum modeling of solvent effects in a twisted intramolecular charge transfer system: The 4-N,N-dimethylaminobenzonitrile (DMABN) molecule. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2018, 201 , 73-81. https://doi.org/10.1016/j.saa.2018.04.064
    12. . Medium Effect on ICT Process: Theory and Experiments. 2018, 115-148. https://doi.org/10.1002/9783527801916.ch4
    13. Arkadiusz Matwijczuk, Andrzej Górecki, Marcin Makowski, Katarzyna Pustuła, Alicja Skrzypek, Joanna Waś, Andrzej Niewiadomy, Mariusz Gagoś. Spectroscopic and Theoretical Studies of Fluorescence Effects in 2-Methylamino-5-(2,4-dihydroxyphenyl)-1,3,4-thiadiazole Induced by Molecular Aggregation. Journal of Fluorescence 2018, 28 (1) , 65-77. https://doi.org/10.1007/s10895-017-2175-2
    14. Poojan Milan Gharat, Sukumaran Muralidharan, Mahesh Sundararajan, Haridas Pal, Sharmistha Dutta Choudhury. Polarity‐Dependant Intramolecular Charge Transfer Characteristics of 9‐Cyano‐10‐(1H‐pyrrol‐1‐yl)anthracene: Photophysical Investigations. ChemistrySelect 2017, 2 (30) , 9751-9759. https://doi.org/10.1002/slct.201701916
    15. Jan-Michael Mewes, John M. Herbert, Andreas Dreuw. On the accuracy of the general, state-specific polarizable-continuum model for the description of correlated ground- and excited states in solution. Physical Chemistry Chemical Physics 2017, 19 (2) , 1644-1654. https://doi.org/10.1039/C6CP05986D
    16. Mercedes V. Bohnwagner, Irene Burghardt, Andreas Dreuw. Regular and red-shifted fluorescence of the donor–acceptor compound 5-(1H-pyrrole-1-yl)thiophenecarbonitrile (TCN) is efficiently quenched by internal modes of thiophene. Physical Chemistry Chemical Physics 2017, 19 (21) , 13951-13959. https://doi.org/10.1039/C7CP01460K

    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2016, 120, 1, 14–27
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.5b09115
    Published December 6, 2015
    Copyright © 2015 American Chemical Society

    Article Views

    828

    Altmetric

    -

    Citations

    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.