Sterically Encumbered Aryl Isocyanides Extend Excited-State Lifetimes and Improve the Photocatalytic Performance of Three-Coordinate Copper(I) β-Diketiminate Charge-Transfer Chromophores

Kim, Dooyoung; Teets, Thomas S.

doi:10.1021/jacs.4c05180

Sterically Encumbered Aryl Isocyanides Extend Excited-State Lifetimes and Improve the Photocatalytic Performance of Three-Coordinate Copper(I) β-Diketiminate Charge-Transfer Chromophores

Journal Article · Mon Jun 10 00:00:00 EDT 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c05180· OSTI ID:2439769

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University of Houston, TX (United States); University of Houson
University of Houston, TX (United States)

Copper(I) complexes are prominent candidates to replace noble metal-based photosensitizers. We recently introduced a three-coordinate design for copper(I) charge-transfer chromophores that pair β-diketiminate ligands with aryl isocyanides. The excited-state lifetime in these compounds can be extended using a bichromophoric “triplet reservoir” strategy, which comes at the expense of a decrease in excited-state energy and reducing power. In this work, we introduce a complementary, sterically driven strategy for increasing the excited-state lifetimes of these photosensitizers, which gives a higher-energy, more strongly reducing charge-transfer triplet state than does the bichromophore approach. The compounds presented (Cu1–Cu4) have the general formula Cu(CyNacNac^Me)(CN-Ar), where CyNacNac^Me is a cyclohexyl-substituted β-diketiminate and CN-Ar is an aryl isocyanide with a variable steric profile. Their structural features and electrochemical and photophysical properties are described. The complexes with sterically encumbered 2,6-diisopropylphenyl or m-terphenyl isocyanide ligands (Cu2–Cu4) exhibit prolonged excited-state lifetimes relative to those of the parent 2,6-dimethylphenyl isocyanide compound Cu1. Specifically, one of the m-terphenyl isocyanide compounds, Cu3, displays an excited-state lifetime of 276 ns, approximately 30 times longer than that of Cu1 (9.3 ns). The photoluminescence quantum yield of Cu3 (0.09) also increases by two orders of magnitude compared to that of Cu1 (0.0008). Furthermore, the strong excited-state reducing power (*E^ox = –2.4 V vs Fc^+/0) and long lifetime of Cu3 lead to higher yields in photoredox and photocatalytic isomerization reactions, which include dehalogenation and/or hydrodgenation of benzophenone substrates, C–O bond activation of a lignin model substrate, and photocatalytic E/Z isomerization of stilbene.

View Accepted Manuscript (DOE)

Research Organization:: University of Houston, TX (United States)

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

Grant/Contract Number:: SC0023394

OSTI ID:: 2439769

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 24 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (40)

Heteroleptic Copper(I)-Based Complexes for Photocatalysis: Combinatorial Assembly, Discovery, and Optimization Minozzi, Clémentine; Caron, Antoine; Grenier-Petel, Jean-Christophe Angewandte Chemie International Edition, Vol. 57, Issue 19 https://doi.org/10.1002/anie.201800144	journal	April 2018
Air‐Stable Blue Phosphorescent Tetradentate Platinum(II) Complexes as Strong Photo‐Reductant Li, Kai; Wan, Qingyun; Yang, Chen Angewandte Chemie International Edition, Vol. 57, Issue 43 https://doi.org/10.1002/anie.201808642	journal	October 2018
Samb V ca: A Web Application for the Calculation of the Buried Volume of N-Heterocyclic Carbene Ligands Poater, Albert; Cosenza, Biagio; Correa, Andrea European Journal of Inorganic Chemistry, Vol. 2009, Issue 13 https://doi.org/10.1002/ejic.200801160	journal	May 2009
Emerging Organic Photoredox Catalysts for Organic Transformations Lee, Yungyeong; Kwon, Min Sang European Journal of Organic Chemistry, Vol. 2020, Issue 38 https://doi.org/10.1002/ejoc.202000720	journal	August 2020
Light-driven catalytic conversion of CO2 with heterogenized molecular catalysts based on fourth period transition metals Perazio, Alessandro; Lowe, Grace; Gobetto, Roberto Coordination Chemistry Reviews, Vol. 443 https://doi.org/10.1016/j.ccr.2021.214018	journal	September 2021
Syntheses and structures of bis(2,6-xylyl-nacnac) copper(I) complexes Oguadinma, Paul O.; Schaper, Frank Inorganica Chimica Acta, Vol. 362, Issue 2 https://doi.org/10.1016/j.ica.2008.05.008	journal	January 2009
Steric and electronic effects in the bonding of N-heterocyclic ligands to transition metals Cavallo, Luigi; Correa, Andrea; Costabile, Chiara Journal of Organometallic Chemistry, Vol. 690, Issue 24-25 https://doi.org/10.1016/j.jorganchem.2005.07.012	journal	December 2005
Advances in the light conversion properties of Cu(I)-based photosensitizers Lazorski, Megan S.; Castellano, Felix N. Polyhedron, Vol. 82 https://doi.org/10.1016/j.poly.2014.04.060	journal	November 2014
A series of four-coordinate heteroleptic copper(I) complexes with diimine and β-diketiminate ligands Kim, Dooyoung; Teets, Thomas S. Polyhedron, Vol. 248, p. 116748 https://doi.org/10.1016/j.poly.2023.116748	journal	November 2023
Amine Functionalization via Oxidative Photoredox Catalysis: Methodology Development and Complex Molecule Synthesis Beatty, Joel W.; Stephenson, Corey R. J. Accounts of Chemical Research, Vol. 48, Issue 5 https://doi.org/10.1021/acs.accounts.5b00068	journal	May 2015
Judicious Design of Cationic, Cyclometalated Ir(III) Complexes for Photochemical Energy Conversion and Optoelectronics Mills, Isaac N.; Porras, Jonathan A.; Bernhard, Stefan Accounts of Chemical Research, Vol. 51, Issue 2 https://doi.org/10.1021/acs.accounts.7b00375	journal	January 2018
Catalytic Lignin Depolymerization to Aromatic Chemicals Zhang, Chaofeng; Wang, Feng Accounts of Chemical Research, Vol. 53, Issue 2 https://doi.org/10.1021/acs.accounts.9b00573	journal	January 2020
Advances in the E → Z Isomerization of Alkenes Using Small Molecule Photocatalysts Neveselý, Tomáš; Wienhold, Max; Molloy, John J. Chemical Reviews https://doi.org/10.1021/acs.chemrev.1c00324	journal	August 2021
Photoactive Copper Complexes: Properties and Applications Beaudelot, Jérôme; Oger, Samuel; Peruško, Stefano Chemical Reviews, Vol. 122, Issue 22 https://doi.org/10.1021/acs.chemrev.2c00033	journal	November 2022
Dual Catalysis Strategies in Photochemical Synthesis Skubi, Kazimer L.; Blum, Travis R.; Yoon, Tehshik P. Chemical Reviews, Vol. 116, Issue 17 https://doi.org/10.1021/acs.chemrev.6b00018	journal	April 2016
Bright Side of Lignin Depolymerization: Toward New Platform Chemicals Sun, Zhuohua; Fridrich, Bálint; de Santi, Alessandra Chemical Reviews, Vol. 118, Issue 2 https://doi.org/10.1021/acs.chemrev.7b00588	journal	January 2018
Next Generation Cuprous Phenanthroline MLCT Photosensitizer Featuring Cyclohexyl Substituents Rosko, Michael C.; Wells, Kaylee A.; Hauke, Cory E. Inorganic Chemistry, Vol. 60, Issue 12 https://doi.org/10.1021/acs.inorgchem.1c01242	journal	June 2021
Sterically Encumbered Heteroleptic Copper(I) β-Diketiminate Complexes with Extended Excited-State Lifetimes Kim, Dooyoung; Rosko, Michael C.; Dang, Vinh Q. Inorganic Chemistry, Vol. 62, Issue 41 https://doi.org/10.1021/acs.inorgchem.3c02042	journal	October 2023
High-throughput Synthesis and Screening of Iridium(III) Photocatalysts for the Fast and Chemoselective Dehalogenation of Aryl Bromides Mdluli, Velabo; Diluzio, Stephen; Lewis, Jacqueline ACS Catalysis, Vol. 10, Issue 13 https://doi.org/10.1021/acscatal.0c02247	journal	May 2020
Robust and Long-Lived Excited State Ru(II) Polyimine Photosensitizers Boost Hydrogen Production Guo, Song; Chen, Kai-Kai; Dong, Ru ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b02226	journal	August 2018
Synthesis and Characterization of Strong Cyclometalated Iridium Photoreductants for Application in Photocatalytic Aryl Bromide Hydrodebromination Shon, Jong-Hwa; Sittel, Steven; Teets, Thomas S. ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b02759	journal	August 2019
A survey of Hammett substituent constants and resonance and field parameters Hansch, Corwin.; Leo, A.; Taft, R. W. Chemical Reviews, Vol. 91, Issue 2 https://doi.org/10.1021/cr00002a004	journal	March 1991
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y. Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr100246c	journal	November 2010
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
Three-Coordinate Copper(II)−Phenolate Complexes Jazdzewski, Brian A.; Holland, Patrick L.; Pink, Maren Inorganic Chemistry, Vol. 40, Issue 24 https://doi.org/10.1021/ic010615c	journal	October 2001
Design of a Long-Lifetime, Earth-Abundant, Aqueous Compatible Cu(I) Photosensitizer Using Cooperative Steric Effects McCusker, Catherine E.; Castellano, Felix N. Inorganic Chemistry, Vol. 52, Issue 14 https://doi.org/10.1021/ic401213p	journal	July 2013
Visible-light-mediated conversion of alcohols to halides Dai, Chunhui; Narayanam, Jagan M. R.; Stephenson, Corey R. J. Nature Chemistry, Vol. 3, Issue 2 https://doi.org/10.1038/nchem.949	journal	January 2011
Towards the online computer-aided design of catalytic pockets Falivene, Laura; Cao, Zhen; Petta, Andrea Nature Chemistry, Vol. 11, Issue 10 https://doi.org/10.1038/s41557-019-0319-5	journal	September 2019
Quantifying and understanding the steric properties of N-heterocyclic carbenes Gómez-Suárez, Adrián; Nelson, David J.; Nolan, Steven P. Chemical Communications, Vol. 53, Issue 18 https://doi.org/10.1039/C7CC00255F	journal	January 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
Isonitriles as supporting and non-innocent ligands in metal catalysis Knorn, Matthias; Lutsker, Eugen; Reiser, Oliver Chemical Society Reviews, Vol. 49, Issue 21 https://doi.org/10.1039/D0CS00223B	journal	January 2020
Recent advances in using 4DPAIPN in photocatalytic transformations Singh, Praveen P.; Srivastava, Vishal Organic & Biomolecular Chemistry, Vol. 19, Issue 2 https://doi.org/10.1039/D0OB01884H	journal	January 2021
Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers Shon, Jong-Hwa; Kim, Dooyoung; Rathnayake, Manjula D. Chemical Science, Vol. 12, Issue 11 https://doi.org/10.1039/D0SC06306A	journal	January 2021
Dehalogenation reaction photocatalyzed by homoleptic copper(i) complexes associated with strongly reductive sacrificial donors Gimeno, Lea; Queffélec, Clémence; Mall Haidaraly, Kevin Catalysis Science & Technology, Vol. 11, Issue 18 https://doi.org/10.1039/D1CY01209F	journal	January 2021
Heteroleptic copper(i) charge-transfer chromophores with panchromatic absorption Kim, Dooyoung; Gray, Thomas G.; Teets, Thomas S. Chemical Communications, Vol. 58, Issue 81 https://doi.org/10.1039/D2CC03873K	journal	January 2022
Photocatalytic hydrogen production Teets, Thomas S.; Nocera, Daniel G. Chemical Communications, Vol. 47, Issue 33 https://doi.org/10.1039/c1cc12390d	journal	January 2011
Photophysical Properties and Redox Potentials of Photosensitizers for Organic Photoredox Transformations Teets, Thomas S.; Wu, Yanyu; Kim, Dooyoung Synlett, Vol. 33, Issue 12 https://doi.org/10.1055/a-1390-9065	journal	March 2021
Microwave Spectra and Molecular Structures of Methyl Cyanide and Methyl Isocyanide Kessler, Myer; Ring, Harold; Trambarulo, Ralph Physical Review, Vol. 79, Issue 1 https://doi.org/10.1103/PhysRev.79.54	journal	July 1950
Crystal structure ofp-toluenesulfonylmethyl isocyanide Bano, Huma; Yousuf, Sammer Acta Crystallographica Section E Crystallographic Communications, Vol. 71, Issue 6 https://doi.org/10.1107/S2056989015008816	journal	May 2015
Photocatalysis gets energized by abundant metals Yaltseva, Polina; Wenger, Oliver S. Science, Vol. 382, Issue 6667 https://doi.org/10.1126/science.adk5923	journal	October 2023

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Sterically Encumbered Aryl Isocyanides Extend Excited-State Lifetimes and Improve the Photocatalytic Performance of Three-Coordinate Copper(I) β-Diketiminate Charge-Transfer Chromophores

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