Direct Evidence for Excited Ligand Field State-based Oxidative Photoredox Chemistry of a Cobalt(III) Polypyridyl Photosensitizer

Alowakennu, Micheal M.; Ghosh, Atanu; McCusker, James K.

doi:10.1021/jacs.3c09374

Title: Direct Evidence for Excited Ligand Field State-based Oxidative Photoredox Chemistry of a Cobalt(III) Polypyridyl Photosensitizer

Journal Article · 13 September 2023 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c09374 · OSTI ID:2280824

Alowakennu, Micheal M. ^[1]; Ghosh, Atanu ^[1];

^[1]

Michigan State Univ., East Lansing, MI (United States)

Increasing interest in sustainable chemistry coupled with the quest to explore new reactivity has spurred research on first-row transition metal complexes for potential applications in a variety of settings. One of the more active areas of research is photoredox catalysis, where the synthetically tunable nature of their electronic structures provides a rich palette of options for tailoring their reactivity to a desired chemical transformation. Understanding the mechanism of excited-state reactivity is critical for the informed development of next-generation catalysts, which in turn requires information concerning the propensity of their electronic excited states to engage in the desired electron or energy transfer processes. Herein we provide direct evidence of the highly oxidizing nature of the lowest-energy ligand-field (LF) excited state of a first-row d⁶-low-spin Co(III) photosensitizer [Co(4,4'-Br₂bpy)₃]³⁺ (where 4,4'-Br₂bpy is 4,4'-dibromo-2,2'-bipyridine). The redox potential associated with the LF excited state of the Co(III) complex was bracketed by performing bimolecular quenching studies by using a series of simple organic electron donors. Time-resolved absorption spectroscopy confirmed a dynamic quenching process attributed to reductive quenching of the lowest-energy ligand-field excited state of the Co(III) chromophore. Analysis of the Stern–Volmer plots for each chromophore-quencher pair revealed a limiting value of E_red* ~ 1.25 V vs Fc/Fc⁺ for the metal-centered excited state, which is significantly stronger than that of more commonly employed transition metal-based photoredox agents such as [Ru(bpy)₃]²⁺ (E_red* = 0.32 V vs Fc/Fc⁺) and [Ir(ppy)₂(bpy)]⁺ (E_red* = 0.27 V vs Fc/Fc⁺). Finally, these results suggest that this class of chromophores could find utility in applications requiring the activation of oxidatively resistant organic substrates for photoredox catalysis.

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Research Organization:: Michigan State Univ., East Lansing, MI (United States); Energy Frontier Research Centers (EFRC) (United States). Bioinspired Light-Escalated Chemistry (BioLEC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019370

OSTI ID:: 2280824

Journal Information:: Journal of the American Chemical Society, Vol. 145, Issue 38; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (51)

Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis Prier, Christopher K.; Rankic, Danica A.; MacMillan, David W. C. Chemical Reviews, Vol. 113, Issue 7 https://doi.org/10.1021/cr300503r	journal	March 2013
Shining Light on Photoredox Catalysis: Theory and Synthetic Applications Tucker, Joseph W.; Stephenson, Corey R. J. The Journal of Organic Chemistry, Vol. 77, Issue 4 https://doi.org/10.1021/jo202538x	journal	January 2012
Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis Chan, Amy Y.; Perry, Ian B.; Bissonnette, Noah B. Chemical Reviews, Vol. 122, Issue 2 https://doi.org/10.1021/acs.chemrev.1c00383	journal	November 2021
Merging Photoredox Catalysis with Organocatalysis: The Direct Asymmetric Alkylation of Aldehydes Nicewicz, D. A.; MacMillan, D. W. C. Science, Vol. 322, Issue 5898 https://doi.org/10.1126/science.1161976	journal	October 2008
Asymmetric Photocatalysis with Bis-cyclometalated Rhodium Complexes Huang, Xiaoqiang; Meggers, Eric Accounts of Chemical Research, Vol. 52, Issue 3 https://doi.org/10.1021/acs.accounts.9b00028	journal	March 2019
Photochemistry and photocatalysis of rhenium(I) diimine complexes Takeda, Hiroyuki; Koike, Kazuhide; Morimoto, Tatsuki Advances in Inorganic Chemistry https://doi.org/10.1016/B978-0-12-385904-4.00007-X	book	January 2011
Radical Fluoroalkylation of Isocyanides with Fluorinated Sulfones by Visible‐Light Photoredox Catalysis Rong, Jian; Deng, Ling; Tan, Ping Angewandte Chemie International Edition, Vol. 55, Issue 8 https://doi.org/10.1002/anie.201510533	journal	January 2016
Visible‐Light‐Induced Radical Di‐ and Trifluoromethylation of β, γ‐Unsaturated Oximes: Synthesis of Di‐ and Trifluoromethylated Isoxazolines Zhu, Mei; Fun, Weijun; Guo, Wenbo European Journal of Organic Chemistry, Vol. 2019, Issue 7 https://doi.org/10.1002/ejoc.201801790	journal	January 2019
Visible Light-Induced Transition Metal Catalysis Cheung, Kelvin Pak Shing; Sarkar, Sumon; Gevorgyan, Vladimir Chemical Reviews, Vol. 122, Issue 2 https://doi.org/10.1021/acs.chemrev.1c00403	journal	October 2021
Divergent Photocatalytic Reactions of α-Ketoesters under Triplet Sensitization and Photoredox Conditions Zheng, Jian; Dong, Xiao; Yoon, Tehshik P. Organic Letters, Vol. 22, Issue 16 https://doi.org/10.1021/acs.orglett.0c02314	journal	August 2020
Organic Photoredox Catalysis Romero, Nathan A.; Nicewicz, David A. Chemical Reviews, Vol. 116, Issue 17 https://doi.org/10.1021/acs.chemrev.6b00057	journal	June 2016
Bimolecular reactivity of 3d metal-centered excited states (Cr, Mn, Fe, Co) Förster, Christoph; Heinze, Katja Chemical Physics Reviews, Vol. 3, Issue 4 https://doi.org/10.1063/5.0112531	journal	November 2022
Photoredox Catalysis with Metal Complexes Made from Earth-Abundant Elements Larsen, Christopher B.; Wenger, Oliver S. Chemistry - A European Journal, Vol. 24, Issue 9 https://doi.org/10.1002/chem.201703602	journal	November 2017
Photoredox catalysts based on earth-abundant metal complexes Hockin, Bryony M.; Li, Chenfei; Robertson, Neil Catalysis Science & Technology, Vol. 9, Issue 4 https://doi.org/10.1039/C8CY02336K	journal	January 2019
Photoactive Complexes with Earth-Abundant Metals Wenger, Oliver S. Journal of the American Chemical Society, Vol. 140, Issue 42 https://doi.org/10.1021/jacs.8b08822	journal	September 2018
Photooxidizing Chromium Catalysts for Promoting Radical Cation Cycloadditions Stevenson, Susan M.; Shores, Matthew P.; Ferreira, Eric M. Angewandte Chemie, Vol. 127, Issue 22 https://doi.org/10.1002/ange.201501220	journal	April 2015
Manganese(i) complexes with metal-to-ligand charge transfer luminescence and photoreactivity Herr, Patrick; Kerzig, Christoph; Larsen, Christopher B. Nature Chemistry, Vol. 13, Issue 10 https://doi.org/10.1038/s41557-021-00744-9	journal	August 2021
Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime Kjær, Kasper Skov; Kaul, Nidhi; Prakash, Om Science, Vol. 363, Issue 6424 https://doi.org/10.1126/science.aau7160	journal	November 2018
Accessing Photoredox Transformations with an Iron(III) Photosensitizer and Green Light Aydogan, Akin; Bangle, Rachel E.; Cadranel, Alejandro Journal of the American Chemical Society, Vol. 143, Issue 38 https://doi.org/10.1021/jacs.1c06081	journal	September 2021
Organocatalytic Enantioselective Alkylation of Aldehydes with [Fe(bpy) ₃ ]Br ₂ Catalyst and Visible Light Gualandi, Andrea; Marchini, Marianna; Mengozzi, Luca ACS Catalysis, Vol. 5, Issue 10 https://doi.org/10.1021/acscatal.5b01573	journal	September 2015
Photo‐induced Cobalt‐catalyzed Aerobic N−N Coupling of Diarylamines at Room Temperature Luo, Guanzhong; Han, Yu; Zhang, Ruohan Asian Journal of Organic Chemistry, Vol. 11, Issue 12 https://doi.org/10.1002/ajoc.202200553	journal	November 2022
Copper(II)-Photocatalyzed N–H Alkylation with Alkanes Zheng, Yi-Wen; Narobe, Rok; Donabauer, Karsten ACS Catalysis, Vol. 10, Issue 15 https://doi.org/10.1021/acscatal.0c01924	journal	July 2020
Electronic structure in the transition metal block and its implications for light harvesting McCusker, James K. Science, Vol. 363, Issue 6426 https://doi.org/10.1126/science.aav9104	journal	January 2019
Tracking excited-state charge and spin dynamics in iron coordination complexes Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe Nature, Vol. 509, Issue 7500 https://doi.org/10.1038/nature13252	journal	May 2014
Femtosecond Excited-State Dynamics of an Iron(II) Polypyridyl Solar Cell Sensitizer Model Monat, Jeremy E.; McCusker, James K. Journal of the American Chemical Society, Vol. 122, Issue 17 https://doi.org/10.1021/ja992436o	journal	May 2000
Towards longer-lived metal-to-ligand charge transfer states of iron(ii) complexes: an N-heterocyclic carbene approach Liu, Yizhu; Harlang, Tobias; Canton, Sophie E. Chemical Communications, Vol. 49, Issue 57 https://doi.org/10.1039/c3cc43833c	journal	January 2013
A Modular Approach to Light Capture and Synthetic Tuning of the Excited-State Properties of Fe(II)-Based Chromophores Paulus, Bryan C.; Nielsen, Karl C.; Tichnell, Christopher R. Journal of the American Chemical Society, Vol. 143, Issue 21 https://doi.org/10.1021/jacs.1c02451	journal	May 2021
Iron(ii) coordination complexes with panchromatic absorption and nanosecond charge-transfer excited state lifetimes Braun, Jason D.; Lozada, Issiah B.; Kolodziej, Charles Nature Chemistry, Vol. 11, Issue 12 https://doi.org/10.1038/s41557-019-0357-z	journal	November 2019
Visible‐Light Induced Fixation of SO₂ into Organic Molecules with Polypyridine Chromium(III) Complexes Sittel, Steven; Sell, Arne Christian; Hofmann, Kamil ChemCatChem, Vol. 15, Issue 6 https://doi.org/10.1002/cctc.202201562	journal	March 2023
Mechanistic Origin of Photoredox Catalysis Involving Iron(II) Polypyridyl Chromophores Woodhouse, Matthew D.; McCusker, James K. Journal of the American Chemical Society, Vol. 142, Issue 38 https://doi.org/10.1021/jacs.0c08389	journal	September 2020
Shedding Light on the Oxidizing Properties of Spin-Flip Excited States in a Cr^III Polypyridine Complex and Their Use in Photoredox Catalysis Bürgin, Tobias H.; Glaser, Felix; Wenger, Oliver S. Journal of the American Chemical Society, Vol. 144, Issue 31 https://doi.org/10.1021/jacs.2c04465	journal	August 2022
Photo‐Chromium: Sensitizer for Visible‐Light‐Induced Oxidative C−H Bond Functionalization—Electron or Energy Transfer? Otto, Sven; Nauth, Alexander M.; Ermilov, Eugenyi ChemPhotoChem, Vol. 1, Issue 8 https://doi.org/10.1002/cptc.201700077	journal	June 2017
³ d-d Excited States of Ni(II) Complexes Relevant to Photoredox Catalysis: Spectroscopic Identification and Mechanistic Implications Ting, Stephen I.; Garakyaraghi, Sofia; Taliaferro, Chelsea M. Journal of the American Chemical Society, Vol. 142, Issue 12 https://doi.org/10.1021/jacs.0c00781	journal	March 2020
Correlations between electrochemical potentials and optical charge transfer energies in ruthenium bipyridine derivatives Dodsworth, Elaine S.; Lever, A. B. P. Chemical Physics Letters, Vol. 124, Issue 2 https://doi.org/10.1016/0009-2614(86)85135-1	journal	February 1986
Ligand-Field Spectroscopy of Co(III) Complexes and the Development of a Spectrochemical Series for Low-Spin d⁶Charge-Transfer Chromophores Yarranton, Jonathan T.; McCusker, James K. Journal of the American Chemical Society, Vol. 144, Issue 27 https://doi.org/10.1021/jacs.2c04945	journal	June 2022
Picosecond excited-state dynamics in octahedral cobalt(III) complexes: intersystem crossing versus internal conversion McCusker, James K.; Walda, Kevin N.; Magde, Douglas Inorganic Chemistry, Vol. 32, Issue 4 https://doi.org/10.1021/ic00056a010	journal	February 1993
A Fast Transient Absorption Study of Co(AcAc)3 Ferrari, Luisa; Satta, Mauro; Palma, Amedeo Frontiers in Chemistry, Vol. 7 https://doi.org/10.3389/fchem.2019.00348	journal	May 2019
Microsecond Photoluminescence and Photoreactivity of a Metal-Centered Excited State in a Hexacarbene–Co(III) Complex Kaufhold, Simon; Rosemann, Nils W.; Chábera, Pavel Journal of the American Chemical Society, Vol. 143, Issue 3 https://doi.org/10.1021/jacs.0c12151	journal	January 2021
Ballistic ΔS = 2 intersystem crossing in a cobalt cubane following ligand-field excitation probed by extreme ultraviolet spectroscopy Shari'ati, Yusef; Vura-Weis, Josh Physical Chemistry Chemical Physics, Vol. 23, Issue 47 https://doi.org/10.1039/D1CP04136C	journal	January 2021
Cobalt(III) Carbene Complex with an Electronic Excited-State Structure Similar to Cyclometalated Iridium(III) Compounds Sinha, Narayan; Pfund, Björn; Wegeberg, Christina Journal of the American Chemical Society, Vol. 144, Issue 22 https://doi.org/10.1021/jacs.2c02592	journal	May 2022
Blue-Emissive Cobalt(III) Complexes and Their Use in the Photocatalytic Trifluoromethylation of Polycyclic Aromatic Hydrocarbons Pal, Amlan K.; Li, Chenfei; Hanan, Garry S. Angewandte Chemie International Edition, Vol. 57, Issue 27 https://doi.org/10.1002/anie.201802532	journal	June 2018
Highly Efficient and Selective Photocatalytic CO ₂ Reduction to CO in Water by a Cobalt Porphyrin Molecular Catalyst Call, Arnau; Cibian, Mihaela; Yamamoto, Keiya ACS Catalysis, Vol. 9, Issue 6 https://doi.org/10.1021/acscatal.8b04975	journal	April 2019
Visible Light-Gated Cobalt Catalysis for a Spatially and Temporally Resolved [2+2+2] Cycloaddition Ruhl, Kyle E.; Rovis, Tomislav Journal of the American Chemical Society, Vol. 138, Issue 48 https://doi.org/10.1021/jacs.6b08792	journal	November 2016
Photoinduced Cobalt-Catalyzed Desymmetrization of Dialdehydes to Access Axial Chirality Jiang, Hao; He, Xiang-Kui; Jiang, Xuan Journal of the American Chemical Society, Vol. 145, Issue 12 https://doi.org/10.1021/jacs.3c00462	journal	March 2023
The Merger of Photoredox and Cobalt Catalysis Kojima, Masahiro; Matsunaga, Shigeki Trends in Chemistry, Vol. 2, Issue 5 https://doi.org/10.1016/j.trechm.2020.01.004	journal	May 2020
Kinetik und Mechanismus der Elektronübertragung bei der Fluoreszenzlöschung in Acetonitril Rehm, Dieter; Weller, Albert Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 73, Issue 8-9 https://doi.org/10.1002/bbpc.19690730818	journal	October 1969
Estimation of excited-state redox potentials by electron-transfer quenching. Application of electron-transfer theory to excited-state redox processes Bock, C. R.; Connor, J. A.; Gutierrez, A. R. Journal of the American Chemical Society, Vol. 101, Issue 17 https://doi.org/10.1021/ja00511a007	journal	August 1979
The photophysics of photoredox catalysis: a roadmap for catalyst design Arias-Rotondo, Daniela M.; McCusker, James K. Chemical Society Reviews, Vol. 45, Issue 21 https://doi.org/10.1039/C6CS00526H	journal	January 2016
Angular Momentum Conservation in Dipolar Energy Transfer Guo, D.; Knight, T. E.; McCusker, J. K. Science, Vol. 334, Issue 6063 https://doi.org/10.1126/science.1211459	journal	December 2011
Electron Transfer Reaction from Triplet 1,4-Dimethoxybenzene to Hydronium Ion in Aqueous Solution Tajima, So; Tobita, Seiji; Shizuka, Haruo The Journal of Physical Chemistry A, Vol. 103, Issue 31 https://doi.org/10.1021/jp990743a	journal	July 1999
Enhanced Luminescent Iridium(III) Complexes Bearing Aryltriazole Cyclometallated Ligands Ladouceur, Sébastien; Fortin, Daniel; Zysman-Colman, Eli Inorganic Chemistry, Vol. 50, Issue 22 https://doi.org/10.1021/ic2014013	journal	November 2011

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14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Charge transfer
Chromophores
Excited states
Quenching
Redox reactions

Title: Direct Evidence for Excited Ligand Field State-based Oxidative Photoredox Chemistry of a Cobalt(III) Polypyridyl Photosensitizer

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References (51)

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