Anti-Arrhenius behavior of electron transfer reactions in molecular dimers

Lin, Neo; Mani, Tomoyasu

doi:10.1039/d3sc03609j

Title: Anti-Arrhenius behavior of electron transfer reactions in molecular dimers

Journal Article · 29 October 2023 · Chemical Science

DOI: https://doi.org/10.1039/d3sc03609j · OSTI ID:2281332

^[1];

^[2]

Univ. of Connecticut, Storrs, CT (United States)
Univ. of Connecticut, Storrs, CT (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Rates of chemical reactions typically accelerate as the temperature rises, following the Arrhenius law. However, electron transfer reactions may exhibit weak temperature dependence or counterintuitive behavior, known as anti-Arrhenius behavior, wherein reaction rates decrease as temperature increases. Solvent reorganization energy and torsion-induced changes in electronic couplings could contribute to this unusual behavior, but how each contributes to the overall temperature dependence is unclear. One can decelerate the charge recombination process in photogenerated radical pairs or charge-separated states by harnessing this often-overlooked phenomenon. This means that we could achieve long-lived radical pairs without relying on conventional cooling. Using a series of homo molecular dimers, we showed that the degree of torsional hindrance dictates temperature-dependent torsion-induced changes in electronic coupling and, therefore, charge recombination rates. The overall temperature dependence is controlled by how changes in electronic coupling and the temperature-dependent solvent reorganization energy contribute to the rates of charge recombination. Our findings pave the way for rationally designing molecules that exhibit anti-Arrhenius behavior to slow down charge recombination, opening possibilities for applications in energy-related and quantum information technologies.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: SC0012704

OSTI ID:: 2281332

Report Number(s):: BNL--225164-2024-JAAM

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 45 Vol. 14; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

BisBODIPY as PCT-based halogen free photosensitizers for highly efficient excited triplet state and singlet oxygen formation: Tuning the efficiency by different linking positions Zhang, Xian-Fu Dyes and Pigments, Vol. 146 https://doi.org/10.1016/j.dyepig.2017.07.051	journal	November 2017
A Failure of Continuum Theory: Temperature Dependence of the Solvent Reorganization Energy of Electron Transfer in Highly Polar Solvents Vath, Peter; Zimmt, Matthew B.; Matyushov, Dmitry V. The Journal of Physical Chemistry B, Vol. 103, Issue 43 https://doi.org/10.1021/jp990494q	journal	October 1999
Controlling Symmetry Breaking Charge Transfer in BODIPY Pairs Estergreen, Laura; Mencke, Austin R.; Cotton, Daniel E. Accounts of Chemical Research, Vol. 55, Issue 11 https://doi.org/10.1021/acs.accounts.2c00044	journal	May 2022
Controlling the Adiabaticity of Electron-Transfer Reactions Using Nematic Liquid-Crystal Solvents Wiederrecht, Gary P.; Svec, Walter A.; Wasielewski, Michael R. The Journal of Physical Chemistry B, Vol. 103, Issue 9 https://doi.org/10.1021/jp983907g	journal	March 1999
Intramolecular Excimer Formation for Covalently Linked Boron Dipyrromethene Dyes Alamiry, Mohammed A. H.; Benniston, Andrew C.; Copley, Graeme The Journal of Physical Chemistry A, Vol. 115, Issue 44 https://doi.org/10.1021/jp2070419	journal	October 2011
Null Exciton-Coupled Chromophoric Dimer Exhibits Symmetry-Breaking Charge Separation Sebastian, Ebin; Hariharan, Mahesh Journal of the American Chemical Society, Vol. 143, Issue 34 https://doi.org/10.1021/jacs.1c05793	journal	August 2021
Intersystem Crossing Mediated by Photoinduced Intramolecular Charge Transfer: Julolidine−Anthracene Molecules with Perpendicular π Systems Dance, Zachary E. X.; Mickley, Sarah M.; Wilson, Thea M. The Journal of Physical Chemistry A, Vol. 112, Issue 18 https://doi.org/10.1021/jp800561g	journal	May 2008
Symmetry-Breaking Charge Transfer in Boron Dipyridylmethene (DIPYR) Dimers Golden, Jessica H.; Estergreen, Laura; Porter, Tyler ACS Applied Energy Materials, Vol. 1, Issue 3 https://doi.org/10.1021/acsaem.7b00214	journal	February 2018
Electron Transfer-from Isolated Molecules to Biomolecules Bixon, M.; Jortner, Joshua Advances in Chemical Physics https://doi.org/10.1002/9780470141656.ch3	book	January 2007
Formation of Glasses from Liquids and Biopolymers Angell, C. A. Science, Vol. 267, Issue 5206 https://doi.org/10.1126/science.267.5206.1924	journal	March 1995
Solar Fuels via Artificial Photosynthesis Gust, Devens; Moore, Thomas A.; Moore, Ana L. Accounts of Chemical Research, Vol. 42, Issue 12 https://doi.org/10.1021/ar900209b	journal	December 2009
Electron transfer reactions in chemistry. Theory and experiment Marcus, Rudolph A. Reviews of Modern Physics, Vol. 65, Issue 3, p. 599-610 https://doi.org/10.1103/RevModPhys.65.599	journal	July 1993
Bell-shaped temperature dependence in quenching of excited Ru(bpy)32+ by an organic acceptor Kim, Haeng Boo; Kitamura, Noboru; Kawanishi, Yuji Journal of the American Chemical Society, Vol. 109, Issue 8 https://doi.org/10.1021/ja00242a042	journal	April 1987
Photogenerated Spin-Correlated Radical Pairs: From Photosynthetic Energy Transduction to Quantum Information Science Harvey, Samantha M.; Wasielewski, Michael R. Journal of the American Chemical Society, Vol. 143, Issue 38 https://doi.org/10.1021/jacs.1c07706	journal	September 2021
Solvent relaxation dynamics and electron transfer Bixon, M.; Jortner, Joshua Chemical Physics, Vol. 176, Issue 2-3 https://doi.org/10.1016/0301-0104(93)80255-8	journal	October 1993
Molecular Rotor Measures Viscosity of Live Cells via Fluorescence Lifetime Imaging Kuimova, Marina K.; Yahioglu, Gokhan; Levitt, James A. Journal of the American Chemical Society, Vol. 130, Issue 21 https://doi.org/10.1021/ja800570d	journal	May 2008
Time-Resolved EPR Study of Photoexcited Triplet-State Formation in Electron-Donor-Substituted Acridinium Ions van Willigen, Hans; Jones, Guilford; Farahat, Mohammad S. The Journal of Physical Chemistry, Vol. 100, Issue 9 https://doi.org/10.1021/jp953176+	journal	January 1996
Bimolecular Recombination in Organic Photovoltaics Lakhwani, Girish; Rao, Akshay; Friend, Richard H. Annual Review of Physical Chemistry, Vol. 65, Issue 1 https://doi.org/10.1146/annurev-physchem-040513-103615	journal	April 2014
Photoinduced Symmetry-Breaking Charge Separation Vauthey, Eric ChemPhysChem, Vol. 13, Issue 8 https://doi.org/10.1002/cphc.201200106	journal	March 2012
Effect of ring torsion on intramolecular vibrational redistribution dynamics of 1,1′-binaphthyl and 2,2′-binaphthyl Lee, Nam Ki; Park, Soonyong; Yoon, Myung-Han Phys. Chem. Chem. Phys., Vol. 14, Issue 2 https://doi.org/10.1039/C1CP22854D	journal	January 2012
Controlling Electron Transfer through the Manipulation of Structure and Ligand-Based Torsional Motions: A Computational Exploration of Ruthenium Donor−Acceptor Systems using Density Functional Theory Meylemans, Heather A.; Damrauer, Niels H. Inorganic Chemistry, Vol. 48, Issue 23 https://doi.org/10.1021/ic901637b	journal	October 2009
The effect of intramolecular quantum modes on free energy relationships for electron transfer reactions Ulstrup, Jens; Jortner, Joshua The Journal of Chemical Physics, Vol. 63, Issue 10 https://doi.org/10.1063/1.431152	journal	November 1975
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
Activationless and pseudoactivationless primary electron transfer in photosynthetic bacterial reaction centers Bixon, M.; Jortner, Joshua Chemical Physics Letters, Vol. 159, Issue 1 https://doi.org/10.1016/S0009-2614(89)87445-7	journal	June 1989
Dimers of Dipyrrometheneboron Difluoride (BODIPY) with Light Spectroscopic Applications in Chemistry and Biology Bergström, Fredrik; Mikhalyov, Ilya; Hägglöf, Peter Journal of the American Chemical Society, Vol. 124, Issue 2 https://doi.org/10.1021/ja010983f	journal	January 2002
Symmetry-Breaking Charge Separation in Molecular Constructs for Efficient Light Energy Conversion Sebastian, Ebin; Hariharan, Mahesh ACS Energy Letters, Vol. 7, Issue 2 https://doi.org/10.1021/acsenergylett.1c02412	journal	January 2022
Energetics of Electron-Transfer Reactions in Soft Condensed Media Matyushov, Dmitry V. Accounts of Chemical Research, Vol. 40, Issue 4 https://doi.org/10.1021/ar7000167	journal	April 2007
Molecular Mechanisms of Photosynthesis Blankenship, Robert E. https://doi.org/10.1002/9780470758472	book	December 2002
Molecular qubits based on photogenerated spin-correlated radical pairs for quantum sensing Mani, Tomoyasu Chemical Physics Reviews, Vol. 3, Issue 2 https://doi.org/10.1063/5.0084072	journal	June 2022
Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules Waskasi, Morteza M.; Newton, Marshall D.; Matyushov, Dmitry V. The Journal of Physical Chemistry B, Vol. 121, Issue 12 https://doi.org/10.1021/acs.jpcb.7b00140	journal	March 2017
Gated electron transfer: when are observed rates controlled by conformational interconversion? Hoffman, Brian M.; Ratner, Mark A. Journal of the American Chemical Society, Vol. 109, Issue 21 https://doi.org/10.1021/ja00255a003	journal	October 1987
Marcus Bell-Shaped Electron Transfer Kinetics Observed in an Arrhenius Plot Waskasi, Morteza M.; Kodis, Gerdenis; Moore, Ana L. Journal of the American Chemical Society, Vol. 138, Issue 29 https://doi.org/10.1021/jacs.6b04777	journal	July 2016
Temperature-independent long-range electron transfer reactions in the Marcus inverted region Liang, Nong; Miller, John R.; Closs, Gerhard L. Journal of the American Chemical Society, Vol. 112, Issue 13 https://doi.org/10.1021/ja00169a054	journal	June 1990
Conformational Gating of Long Distance Electron Transfer through Wire-like Bridges in Donor−Bridge−Acceptor Molecules Davis, William B.; Ratner, Mark A.; Wasielewski, Michael R. Journal of the American Chemical Society, Vol. 123, Issue 32 https://doi.org/10.1021/ja010330z	journal	August 2001
Rates of primary electron transfer in photosynthetic reaction centres and their mechanistic implications Fleming, G. R.; Martin, J. L.; Breton, J. Nature, Vol. 333, Issue 6169 https://doi.org/10.1038/333190a0	journal	May 1988
On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I Marcus, R. A. The Journal of Chemical Physics, Vol. 24, Issue 5 https://doi.org/10.1063/1.1742723	journal	May 1956
Fully Functionalizable β,β′-BODIPY Dimer: Synthesis, Structure, and Photophysical Signatures Arroyo-Córdoba, Ismael J.; Sola-Llano, Rebeca; Epelde-Elezcano, Nerea The Journal of Organic Chemistry, Vol. 83, Issue 17 https://doi.org/10.1021/acs.joc.8b01429	journal	August 2018
Cofacial Boron Dipyrromethene (Bodipy) Dimers: Synthesis, Charge Delocalization, and Exciton Coupling Benniston, Andrew C.; Copley, Graeme; Harriman, Anthony The Journal of Organic Chemistry, Vol. 75, Issue 6 https://doi.org/10.1021/jo1000803	journal	February 2010
Contemporary Issues in Electron Transfer Research Barbara, Paul F.; Meyer, Thomas J.; Ratner, Mark A. The Journal of Physical Chemistry, Vol. 100, Issue 31 https://doi.org/10.1021/jp9605663	journal	January 1996
Mixed Electronic States in Molecular Dimers: Connecting Singlet Fission, Excimer Formation, and Symmetry-Breaking Charge Transfer Young, Ryan M.; Wasielewski, Michael R. Accounts of Chemical Research, Vol. 53, Issue 9 https://doi.org/10.1021/acs.accounts.0c00397	journal	August 2020
Excimer emission and energy transfer in cofacial boradiazaindacene (BODIPY) dimers built on a xanthene scaffold Saki, Neslihan; Dinc, Tarik; Akkaya, Engin U. Tetrahedron, Vol. 62, Issue 11 https://doi.org/10.1016/j.tet.2005.12.021	journal	March 2006
Spin-Allowed Transitions Control the Formation of Triplet Excited States in Orthogonal Donor-Acceptor Dyads Buck, Jason T.; Boudreau, Andrew M.; DeCarmine, André Chem, Vol. 5, Issue 1 https://doi.org/10.1016/j.chempr.2018.10.001	journal	January 2019
Über die Reaktionsgeschwindigkeit bei der Inversion von Rohrzucker durch Säuren Arrhenius, Svante Zeitschrift für Physikalische Chemie, Vol. 4U, Issue 1 https://doi.org/10.1515/zpch-1889-0416	journal	January 1889
The crystal structures, spectrometric, photodynamic properties and bioimaging of β-β linked Bodipy oligomers Li, Zhensheng; Liu, Yang; Hou, Xufeng Journal of Luminescence, Vol. 212 https://doi.org/10.1016/j.jlumin.2019.04.030	journal	August 2019
Time-Resolved EPR Studies of Photogenerated Radical Ion Pairs Separated by p -Phenylene Oligomers and of Triplet States Resulting from Charge Recombination ^† Dance, Zachary E. X.; Mi, Qixi; McCamant, David W. The Journal of Physical Chemistry B, Vol. 110, Issue 50 https://doi.org/10.1021/jp063690n	journal	December 2006
Common Features of Extraordinary Rate Theories Peters, Baron The Journal of Physical Chemistry B, Vol. 119, Issue 21 https://doi.org/10.1021/acs.jpcb.5b02547	journal	May 2015
Exploiting Conformational Dynamics of Structurally Tuned Aryl-Substituted Terpyridyl Ruthenium(II) Complexes to Inhibit Charge Recombination in Dye-Sensitized Solar Cells Spettel, Karen E.; Damrauer, Niels H. The Journal of Physical Chemistry C, Vol. 120, Issue 20 https://doi.org/10.1021/acs.jpcc.6b03302	journal	May 2016
A Spectroscopic Study of Solvent Reorganization Energy: Dependence on Temperature, Charge Transfer Distance, and the Type of Solute−Solvent Interactions Vath, Peter; Zimmt, Matthew B. The Journal of Physical Chemistry A, Vol. 104, Issue 12 https://doi.org/10.1021/jp993667k	journal	March 2000
Structural Control of the Photodynamics of Boron−Dipyrrin Complexes Kee, Hooi Ling; Kirmaier, Christine; Yu, Lianhe The Journal of Physical Chemistry B, Vol. 109, Issue 43 https://doi.org/10.1021/jp0525078	journal	November 2005
Intersystem Crossing Involving Strongly Spin Exchange-Coupled Radical Ion Pairs in Donor–bridge–Acceptor Molecules Colvin, Michael T.; Ricks, Annie Butler; Scott, Amy M. The Journal of Physical Chemistry A, Vol. 116, Issue 8 https://doi.org/10.1021/jp212546w	journal	February 2012

Similar Records

Final Report on project Photoinduced Dipoles and Charge Pairs in Condensed Media

Technical Report · 2006 · OSTI ID:892091

Braun, Charles L

Radiation Laboratory quarterly report, January 1, 1978--March 31, 1978. NDRL--1877

Technical Report · 1978 · OSTI ID:6939690

Dependence of rate constants for photoinduced charge separation and dark charge recombination on the free energy of reaction restricted-distance porphyrin-quinone molecules

Journal Article · 1985 · J. Am. Chem. Soc.; (United States) · OSTI ID:7049615

Wasielewski, M R; Niemczyk, M P; Svec, W A; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Anti-Arrhenius behavior of electron transfer reactions in molecular dimers

Citation Formats

References (50)

Similar Records

Related Subjects