ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

H-Aggregation Effects between π-Conjugated Chromophores in Cofacial Dimers and Trimers: Comparison of Theory and Single-Molecule Experiment

  • Christoph Allolio*
    Christoph Allolio
    Institut für Experimentelle und Angewandte Physik  and  Institut für Physikalische und Theoretische Chemie, Universität Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany
    *E-mail: [email protected]
  • Thomas Stangl
    Thomas Stangl
    Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany
  • Theresa Eder
    Theresa Eder
    Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany
    More by Theresa Eder
  • Daniela Schmitz
    Daniela Schmitz
    Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany
  • Jan Vogelsang
    Jan Vogelsang
    Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany
  • Sigurd Höger
    Sigurd Höger
    Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany
  • Dominik Horinek
    Dominik Horinek
    Institut für Physikalische und Theoretische Chemie, Universität Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany
  • , and 
  • John M. Lupton
    John M. Lupton
    Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany
Cite this: J. Phys. Chem. B 2018, 122, 24, 6431–6441
Publication Date (Web):May 9, 2018
https://doi.org/10.1021/acs.jpcb.8b01188
Copyright © 2018 American Chemical Society

    Article Views

    971

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    Excited-state interchromophoric couplings in π-conjugated polymers present a daunting challenge to study as their spectroscopic signatures are difficult to separate from structure-dependent intrachromophoric spectral characteristics. Using custom-designed molecular model systems in combination with single-molecule spectroscopy, a controlled coupling of the excited states between cofacially arranged π-conjugated oligomers is shown to be possible. Multiscale molecular dynamics simulations allow us to generate a representative ensemble of molecular structures of the model molecule embedded in a polymer matrix and examine the connection between structural fluctuations of the molecule with theoretically predicted and measured spectral signatures. The single molecules in the embedding matrix polymer can be assigned to specific conformational features with the help of computer-based “virtual spectroscopy”. By combining a quantum chemical approach with an analytical approach, we show that the coupling between the chromophores is well-described by transition dipole coupling above an interchromophoric separation of ∼4.5 Å. Even for aligned chromophores, however, twisting between repeat units of the π-system and bending of the individual π-systems can lead to a decoupling of the chromophores to a degree far beyond what their equilibrium structures would suggest: tiny displacements of the molecular constituents can dramatically impact excited-state interactions. This observation has profound implications for the design of future tunable organic optoelectronic materials.

    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. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcb.8b01188.

    • Additional details of the synthesis, full characterization of the synthesized compounds, analytical model for the Davydov coupling, comparison of DF-TB and PBE0 optimized geometries and correlation of the unrestricted DF-TB and TD-DFT energies obtained from a single-chromophore trajectory, and benchmark of the π-stacking interactions and torsional deformation energies combined with further computational details (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 12 publications.

    1. Theresa Eder, Daniel Kraus, Sigurd Höger, Jan Vogelsang, John M. Lupton. Vibrations Responsible for Luminescence from HJ-Aggregates of Conjugated Polymers Identified by Cryogenic Spectroscopy of Single Nanoparticles. ACS Nano 2022, 16 (4) , 6382-6393. https://doi.org/10.1021/acsnano.2c00472
    2. Philipp Wilhelm, Jan Vogelsang, Sigurd Höger, John M. Lupton. Homo-FRET in π-Conjugated Polygons: Intermediate-Strength Dipole–Dipole Coupling Makes Energy Transfer Reversible. Nano Letters 2019, 19 (8) , 5483-5488. https://doi.org/10.1021/acs.nanolett.9b01998
    3. Dianelys Ondarse-Alvarez, Tammie Nelson, John M. Lupton, Sergei Tretiak, Sebastian Fernandez-Alberti. Let Digons be Bygones: The Fate of Excitons in Curved π-Systems. The Journal of Physical Chemistry Letters 2018, 9 (24) , 7123-7129. https://doi.org/10.1021/acs.jpclett.8b03160
    4. Yan Long, Xiang Chen, Xiaoxin Pan, Jinxia Duan, Xiaoqing Li, Yongcheng Wu, Jie Tang, Guokun Ma, Liangping Shen, Jun Zhang, Hao Wang. Memristors Constructed by CsPbIBr 2 Inorganic Halide Perovskite for Artificial Synapse and Logic Operation. physica status solidi (RRL) – Rapid Research Letters 2023, 8 https://doi.org/10.1002/pssr.202300342
    5. Susumu Tsuda, Yutaka Nishiyama, Kaito Kawakita, Yumeki Yano, Naoto Yasumura, Shin-ichi Fujiwara. Encapsulation of Cofacial Diarylacetylene Dimers Using [C2]Daisy Chain Rotaxane Strategy. HETEROCYCLES 2023, 106 (12) , 2074. https://doi.org/10.3987/COM-23-14921
    6. Nils Schmickler, David A. Hofmeister, Joshua Bahr, Jakob Schedlbauer, Stefan-S. Jester, John M. Lupton, Sigurd Höger. An Azobenzene-Clamped Bichromophore. Organic Materials 2022, 4 (04) , 153-162. https://doi.org/10.1055/a-1941-7757
    7. Jakob Schedlbauer, Sabrina Streicher, Michael Forster, Ullrich Scherf, Jan Vogelsang, John M. Lupton. Tracking Exciton Diffusion and Exciton Annihilation in Single Nanoparticles of Conjugated Polymers by Photon Correlation Spectroscopy. Advanced Optical Materials 2022, 10 (14) https://doi.org/10.1002/adom.202200092
    8. David Dell’Angelo, Mohammad R. Momeni, Shaina Pearson, Farnaz A. Shakib. Modeling energy transfer and absorption spectra in layered metal–organic frameworks based on a Frenkel–Holstein Hamiltonian. The Journal of Chemical Physics 2022, 156 (4) https://doi.org/10.1063/5.0076640
    9. John M. Lupton, Jan Vogelsang. Photon correlations probe the quantized nature of light emission from optoelectronic materials. Applied Physics Reviews 2021, 8 (4) https://doi.org/10.1063/5.0059764
    10. Yiming Li, Heng Wang, Xiaopeng Li. Over one century after discovery: pyrylium salt chemistry emerging as a powerful approach for the construction of complex macrocycles and metallo-supramolecules. Chemical Science 2020, 11 (45) , 12249-12268. https://doi.org/10.1039/D0SC04585C
    11. Theresa Eder, Jan Vogelsang, Sebastian Bange, Klaas Remmerssen, Daniela Schmitz, Stefan‐S. Jester, Tristan J. Keller, Sigurd Höger, John M. Lupton. Interplay Between J‐ and H‐Type Coupling in Aggregates of π‐Conjugated Polymers: A Single‐Molecule Perspective. Angewandte Chemie 2019, 131 (52) , 19074-19078. https://doi.org/10.1002/ange.201912374
    12. Theresa Eder, Jan Vogelsang, Sebastian Bange, Klaas Remmerssen, Daniela Schmitz, Stefan‐S. Jester, Tristan J. Keller, Sigurd Höger, John M. Lupton. Interplay Between J‐ and H‐Type Coupling in Aggregates of π‐Conjugated Polymers: A Single‐Molecule Perspective. Angewandte Chemie International Edition 2019, 58 (52) , 18898-18902. https://doi.org/10.1002/anie.201912374

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect