A Robust Visible-Light-Harvesting Cyclometalated Ir(III) Diimine Sensitizer for Homogeneous Photocatalytic Hydrogen Production

Yang, Mo; Yarnell, James E.; El Roz, Karim; Castellano, Felix N.

doi:10.1021/acsaem.9b02269

Title: A Robust Visible-Light-Harvesting Cyclometalated Ir(III) Diimine Sensitizer for Homogeneous Photocatalytic Hydrogen Production

Journal Article · 13 January 2020 · ACS Applied Energy Materials

DOI: https://doi.org/10.1021/acsaem.9b02269 · OSTI ID:1633644

^[1]; Yarnell, James E. ^[1]; El Roz, Karim ^[1];

^[1]

North Carolina State Univ., Raleigh, NC (United States)

A cyclometalated Ir(III) diimine complex [Ir(NBI)₂(phen)]PF₆, NBI = 1,8-naphthalenebenzimidizole and phen = 1,10-phenanthroline, exhibits excellent photostability as a sensitizer in a three-component homogeneous aqueous photocatalytic hydrogen producing system. Here, [Co(dmgH)₂(py)Cl] serves as the hydrogen evolving catalyst, and N,N-dimethyl-p-toluidine (DMT) serves as a sacrificial single electron donor. The [Ir(NBI)₂(phen)]PF₆ photosensitizer remained active over the course of 90 h of visible-light-induced (λ_ex = 452 nm, 540 mW) H₂ production photocatalysis, yielding a turnover number (H₂/photosensitizer) of 575 occurring near neutral pH conditions. The proton source was confirmed as being derived from aqueous protons by detecting the headspace gas composition through mass spectrometry in experiments using deuterated water. Mercury metal was used as a selective poisoning test, intended to sequester any metal-based nanomaterial(s) produced in side reactions and provide evidence that the current photocatalytic system was indeed operating in a purely homogeneous manner. Stern–Volmer analyses revealed that reductive quenching by DMT was the dominant (reductive) quenching pathway immediately following light activation in the photocatalytic cycle. The electron-transfer cage escape efficiency for this reaction was measured to be 78%, likely attributable to the significant triplet ligand-centered (³LC) character of the lowest excited-state manifold. Furthermore, this enables the majority of the charged-separated species to enter the subsequent catalytic cycle, thereby enhancing H₂ production. In the presence of the [Co(dmgH)₂(py)Cl] hydrogen evolution catalyst, the one electron reduced species of the ground-state Ir(III) complex transfers an electron to this catalyst with a rate constant of 2.5 × 10⁹ M^–1 s^–1, producing a Co(II) intermediate while regenerating the resting state of the photosensitizer. The combined experimental results indicate numerous benefits in homogeneous photocatalysis become realized when ³LC excited states become involved in excited-state electron-transfer chemistry and can likely be leveraged in future photocatalytic schemes.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: North Carolina State University, Raleigh, NC (United States)

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

Grant/Contract Number:: SC0011979

OSTI ID:: 1633644

Journal Information:: ACS Applied Energy Materials, Vol. 3, Issue 2; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 30 works

Citation information provided by
Web of Science

References (63)

Solar fuels generation and molecular systems: is it homogeneous or heterogeneous catalysis? Artero, Vincent; Fontecave, Marc Chem. Soc. Rev., Vol. 42, Issue 6 https://doi.org/10.1039/C2CS35334B	journal	January 2013
Homogeneous Catalytic System for Photoinduced Hydrogen Production Utilizing Iridium and Rhodium Complexes Cline, Eric D.; Adamson, Samantha E.; Bernhard, Stefan Inorganic Chemistry, Vol. 47, Issue 22 https://doi.org/10.1021/ic800988b	journal	November 2008
[Rh ^III (dmbpy) ₂ Cl ₂ ] ⁺ as a Highly Efficient Catalyst for Visible-Light-Driven Hydrogen Production in Pure Water: Comparison with Other Rhodium Catalysts Stoll, Thibaut; Gennari, Marcello; Serrano, Isabel Chemistry - A European Journal, Vol. 19, Issue 2 https://doi.org/10.1002/chem.201202555	journal	November 2012
Visible Light-Driven Electron Transfer and Hydrogen Generation Catalyzed by Bioinspired [2Fe2S] Complexes Na, Yong; Wang, Mei; Pan, Jingxi Inorganic Chemistry, Vol. 47, Issue 7 https://doi.org/10.1021/ic702010w	journal	April 2008
Homogeneous Photocatalytic H ₂ Production Using a Ru ^II Bathophenanthroline Metal‐to‐Ligand Charge‐Transfer Photosensitizer Khnayzer, Rony S.; Olaiya, Babatunde S.; El Roz, Karim A. ChemPlusChem, Vol. 81, Issue 10 https://doi.org/10.1002/cplu.201600227	journal	October 2016
Discovery and High-Throughput Screening of Heteroleptic Iridium Complexes for Photoinduced Hydrogen Production Goldsmith, Jonas I.; Hudson, William R.; Lowry, Michael S. Journal of the American Chemical Society, Vol. 127, Issue 20 https://doi.org/10.1021/ja0427101	journal	May 2005
Single-Layer Electroluminescent Devices and Photoinduced Hydrogen Production from an Ionic Iridium(III) Complex Lowry, Michael S.; Goldsmith, Jonas I.; Slinker, Jason D. Chemistry of Materials, Vol. 17, Issue 23 https://doi.org/10.1021/cm051312+	journal	October 2005
Photocatalytic H2 Production with a Rhenium/Cobalt System in Water under Acidic Conditions Guttentag, Miguel; Rodenberg, Alexander; Kopelent, René European Journal of Inorganic Chemistry, Vol. 2012, Issue 1 https://doi.org/10.1002/ejic.201100883	journal	November 2011
Robust Cuprous Phenanthroline Sensitizer for Solar Hydrogen Photocatalysis Khnayzer, Rony S.; McCusker, Catherine E.; Olaiya, Babatunde S. Journal of the American Chemical Society, Vol. 135, Issue 38 https://doi.org/10.1021/ja407816f	journal	September 2013
Ultrafast Excited-State Dynamics of Copper(I) Complexes Iwamura, Munetaka; Takeuchi, Satoshi; Tahara, Tahei Accounts of Chemical Research, Vol. 48, Issue 3 https://doi.org/10.1021/ar500353h	journal	February 2015
Transient Absorption Dynamics of Sterically Congested Cu(I) MLCT Excited States Garakyaraghi, Sofia; Danilov, Evgeny O.; McCusker, Catherine E. The Journal of Physical Chemistry A, Vol. 119, Issue 13 https://doi.org/10.1021/acs.jpca.5b00901	journal	March 2015
Enhancing the Visible-Light Absorption and Excited-State Properties of Cu(I) MLCT Excited States Garakyaraghi, Sofia; McCusker, Catherine E.; Khan, Saba Inorganic Chemistry, Vol. 57, Issue 4 https://doi.org/10.1021/acs.inorgchem.7b03169	journal	February 2018
Ultrafast dynamics of ligand-field excited states Juban, Eric A.; Smeigh, Amanda L.; Monat, Jeremy E. Coordination Chemistry Reviews, Vol. 250, Issue 13-14 https://doi.org/10.1016/j.ccr.2006.02.010	journal	July 2006
Photochemical production of hydrogen and oxygen from water: A review and state of the art Amouyal, Edmond Solar Energy Materials and Solar Cells, Vol. 38, Issue 1-4 https://doi.org/10.1016/0927-0248(95)00003-8	journal	January 1995
Photochemical production of hydrogen from water Amouyal, Edmond; Koffi, Philippe Journal of Photochemistry, Vol. 29, Issue 1-2 https://doi.org/10.1016/0047-2670(85)87074-X	journal	May 1985
Homogeneous catalysis of platinum(II) complexes in photochemical hydrogen production from water Sakai, K.; Ozawa, H. Coordination Chemistry Reviews, Vol. 251, Issue 21-24 https://doi.org/10.1016/j.ccr.2007.08.014	journal	November 2007
Visible Light Induced Catalytic Water Reduction without an Electron Relay Tinker, Leonard L.; McDaniel, Neal D.; Curtin, Peter N. Chemistry - A European Journal, Vol. 13, Issue 31 https://doi.org/10.1002/chem.200700480	journal	October 2007
Orchestrated Photocatalytic Water Reduction Using Surface-Adsorbing Iridium Photosensitizers DiSalle, Brian F.; Bernhard, Stefan Journal of the American Chemical Society, Vol. 133, Issue 31 https://doi.org/10.1021/ja201514e	journal	August 2011
Photon-Driven Catalytic Proton Reduction with a Robust Homoleptic Iridium(III) 6-Phenyl-2,2′-bipyridine Complex ([Ir(C ^/\ N ^/\ N) ₂ ] ⁺ ) Tinker, Leonard L.; Bernhard, Stefan Inorganic Chemistry, Vol. 48, Issue 22 https://doi.org/10.1021/ic900777g	journal	November 2009
Structure−Activity Correlations Among Iridium(III) Photosensitizers in a Robust Water-Reducing System Curtin, Peter N.; Tinker, Leonard L.; Burgess, Christine M. Inorganic Chemistry, Vol. 48, Issue 22 https://doi.org/10.1021/ic9007763	journal	July 2009
Highly Efficient Photocatalytic Water Reduction with Robust Iridium(III) Photosensitizers Containing Arylsilyl Substituents Whang, Dong Ryeol; Sakai, Ken; Park, Soo Young Angewandte Chemie International Edition, Vol. 52, Issue 44 https://doi.org/10.1002/anie.201305684	journal	September 2013
[Ir(N^N^N)(C^N)L] ⁺ : A New Family of Luminophores Combining Tunability and Enhanced Photostability Chirdon, Danielle N.; Transue, Wesley J.; Kagalwala, Husain N. Inorganic Chemistry, Vol. 53, Issue 3 https://doi.org/10.1021/ic402411g	journal	January 2014
Metal-complex chromophores for solar hydrogen generation Yuan, Yong-Jun; Yu, Zhen-Tao; Chen, Da-Qin Chemical Society Reviews, Vol. 46, Issue 3 https://doi.org/10.1039/C6CS00436A	journal	January 2017
Tricyclometalated Iridium Complexes as Highly Stable Photosensitizers for Light-Induced Hydrogen Evolution Yuan, Yong-Jun; Yu, Zhen-Tao; Gao, Hong-Lin Chemistry - A European Journal, Vol. 19, Issue 20 https://doi.org/10.1002/chem.201300146	journal	March 2013
Charge-Neutral Amidinate-Containing Iridium Complexes Capable of Efficient Photocatalytic Water Reduction Yu, Zhen-Tao; Yuan, Yong-Jun; Cai, Jian-Guang Chemistry - A European Journal, Vol. 19, Issue 4 https://doi.org/10.1002/chem.201203029	journal	November 2012
Synthetically Tailored Excited States: Phosphorescent, Cyclometalated Iridium(III) Complexes and Their Applications Lowry, Michael S.; Bernhard, Stefan Chemistry - A European Journal, Vol. 12, Issue 31 https://doi.org/10.1002/chem.200600618	journal	October 2006
A new synthetic route to the preparation of a series of strong photoreducing agents: fac-tris-ortho-metalated complexes of iridium(III) with substituted 2-phenylpyridines Dedeian, K.; Djurovich, P. I.; Garces, F. O. Inorganic Chemistry, Vol. 30, Issue 8 https://doi.org/10.1021/ic00008a003	journal	April 1991
Effect of ligand substituents of the d-d luminescence of iridium(III) and rhodium(III) complexes of 1,10-phenanthroline Watts, Richard J.; Van Houten, J. Journal of the American Chemical Society, Vol. 96, Issue 13 https://doi.org/10.1021/ja00820a053	journal	June 1974
Theoretical Studies of the Ground and Excited Electronic States in Cyclometalated Phenylpyridine Ir(III) Complexes Using Density Functional Theory Hay, P. Jeffrey The Journal of Physical Chemistry A, Vol. 106, Issue 8 https://doi.org/10.1021/jp013949w	journal	February 2002
Tracking of Tuning Effects in Bis-Cyclometalated Iridium Complexes: A Combined Time Resolved Infrared Spectroscopy, Electrochemical, and Computational Study Chirdon, Danielle N.; McCusker, Catherine E.; Castellano, Felix N. Inorganic Chemistry, Vol. 52, Issue 15 https://doi.org/10.1021/ic401009q	journal	July 2013
Cationic Bis-cyclometalated Iridium(III) Diimine Complexes and Their Use in Efficient Blue, Green, and Red Electroluminescent Devices Tamayo, Arnold B.; Garon, Simona; Sajoto, Tissa Inorganic Chemistry, Vol. 44, Issue 24 https://doi.org/10.1021/ic050970t	journal	November 2005
Photodriven Electron and Energy Transfer from Copper Phenanthroline Excited States Ruthkosky, Mark; Castellano, Felix N.; Meyer, Gerald J. Inorganic Chemistry, Vol. 35, Issue 22 https://doi.org/10.1021/ic960503z	journal	January 1996
Photoreduction of benzo-1,4-quinone sensitised by metalloporphyrins Harriman, Anthony; Porter, George; Wilowska, Aleksandra Journal of the Chemical Society, Faraday Transactions 2, Vol. 79, Issue 6 https://doi.org/10.1039/f29837900807	journal	January 1983
Visible Light-Driven Hydrogen Production from Aqueous Protons Catalyzed by Molecular Cobaloxime Catalysts Du, Pingwu; Schneider, Jacob; Luo, Genggeng Inorganic Chemistry, Vol. 48, Issue 11 https://doi.org/10.1021/ic900389z	journal	June 2009
A Homogeneous System for the Photogeneration of Hydrogen from Water Based on a Platinum(II) Terpyridyl Acetylide Chromophore and a Molecular Cobalt Catalyst Du, Pingwu; Knowles, Kathryn; Eisenberg, Richard Journal of the American Chemical Society, Vol. 130, Issue 38 https://doi.org/10.1021/ja804650g	journal	September 2008
Proton Electroreduction Catalyzed by Cobaloximes: Functional Models for Hydrogenases Razavet, Mathieu; Artero, Vincent; Fontecave, Marc Inorganic Chemistry, Vol. 44, Issue 13 https://doi.org/10.1021/ic050167z	journal	June 2005
Homogeneous Photocatalytic Hydrogen Production Using π-Conjugated Platinum(II) Arylacetylide Sensitizers Wang, Xianghuai; Goeb, Sébastien; Ji, Zhiqiang Inorganic Chemistry, Vol. 50, Issue 3 https://doi.org/10.1021/ic101731j	journal	February 2011
The electro-oxidation of N,N-dimethyl-p-toluidine in acetonitrile: Rees, Neil V.; Klymenko, Oleksiy V.; Compton, Richard G. Journal of Electroanalytical Chemistry, Vol. 531, Issue 1 https://doi.org/10.1016/S0022-0728(02)01054-9	journal	August 2002
Efficient Phosphorescence from Naphthalenebenzimidizole‐Coordinated Iridium(III) Chromophores Yarnell, James E.; De La Torre, Patricia; Castellano, Felix N. European Journal of Inorganic Chemistry, Vol. 2017, Issue 44 https://doi.org/10.1002/ejic.201700669	journal	September 2017
Parallelization of photocatalytic gas-producing reactions Khnayzer, Rony S.; Martin, Douglas R.; Codding, Charles L. Review of Scientific Instruments, Vol. 86, Issue 3 https://doi.org/10.1063/1.4915349	journal	March 2015
Reductive quenching of ruthenium polypyridyl sensitizers by cyanometalate complexes Mallouk, Thomas E.; Krueger, Jonathan S.; Mayer, James E. Inorganic Chemistry, Vol. 28, Issue 18 https://doi.org/10.1021/ic00317a023	journal	September 1989
Towards a comprehensive understanding of visible-light photogeneration of hydrogen from water using cobalt( ii ) polypyridyl catalysts Khnayzer, R. S.; Thoi, V. S.; Nippe, M. Energy Environ. Sci., Vol. 7, Issue 4 https://doi.org/10.1039/C3EE43982H	journal	January 2014
Homogeneous catalysis of the photoreduction of water by visible light. 2. Mediation by a tris(2,2'-bipyridine)ruthenium(II)-cobalt(II) bipyridine system Krishnan, C. V.; Sutin, Norman Journal of the American Chemical Society, Vol. 103, Issue 8 https://doi.org/10.1021/ja00398a066	journal	April 1981
Synthesis and Photophysical Characterizations of Thermal -Stable Naphthalene Benzimidazoles Erten-Ela, Sule; Ozcelik, Serdar; Eren, Esin Journal of Fluorescence, Vol. 21, Issue 4 https://doi.org/10.1007/s10895-011-0845-z	journal	January 2011
Cyclometalated Iridium(III) Imidazole Phenanthroline Complexes as Luminescent and Electrochemiluminescent G-Quadruplex DNA Binders Castor, Katherine J.; Metera, Kimberly L.; Tefashe, Ushula M. Inorganic Chemistry, Vol. 54, Issue 14 https://doi.org/10.1021/acs.inorgchem.5b00921	journal	June 2015
1,10-Phenanthrolines: versatile building blocks for luminescent molecules, materials and metal complexes Accorsi, Gianluca; Listorti, Andrea; Yoosaf, K. Chemical Society Reviews, Vol. 38, Issue 6 https://doi.org/10.1039/b806408n	journal	January 2009
Synthesis and Characterization of Facial and Meridional Tris-cyclometalated Iridium(III) Complexes Tamayo, Arnold B.; Alleyne, Bert D.; Djurovich, Peter I. Journal of the American Chemical Society, Vol. 125, Issue 24 https://doi.org/10.1021/ja034537z	journal	June 2003
Emission and absorption of Ir(ppy)2(CO)(Cl) – temperature dependence, phosphorescence decay dynamics, and assignment of excited states Finkenzeller, W. J.; Stößel, P.; Yersin, H. Chemical Physics Letters, Vol. 397, Issue 4-6 https://doi.org/10.1016/j.cplett.2004.08.074	journal	October 2004
Highly Phosphorescent Bis-Cyclometalated Iridium Complexes: Synthesis, Photophysical Characterization, and Use in Organic Light Emitting Diodes Lamansky, Sergey; Djurovich, Peter; Murphy, Drew Journal of the American Chemical Society, Vol. 123, Issue 18 https://doi.org/10.1021/ja003693s	journal	May 2001
Insight into the Phosphorescent Process of Cyclometalated Ir(III) Complexes: Combination of the Substituents on Primary and Ancillary Ligands Controls the Emission Rule and Quantum Yield Zhang, Qing; Wang, Xin; Zhang, Yue The Journal of Physical Chemistry C, Vol. 120, Issue 48 https://doi.org/10.1021/acs.jpcc.6b07562	journal	November 2016
Reductive Side of Water Splitting in Artificial Photosynthesis: New Homogeneous Photosystems of Great Activity and Mechanistic Insight McCormick, Theresa M.; Calitree, Brandon D.; Orchard, Alexandra Journal of the American Chemical Society, Vol. 132, Issue 44 https://doi.org/10.1021/ja1057357	journal	November 2010
Photocatalytic H ₂ Production from Water with Rhenium and Cobalt Complexes Probst, Benjamin; Guttentag, Miguel; Rodenberg, Alexander Inorganic Chemistry, Vol. 50, Issue 8 https://doi.org/10.1021/ic102317u	journal	April 2011
Impact of Ligand Exchange in Hydrogen Production from Cobaloxime-Containing Photocatalytic Systems McCormick, Theresa M.; Han, Zhiji; Weinberg, David J. Inorganic Chemistry, Vol. 50, Issue 21 https://doi.org/10.1021/ic2010166	journal	November 2011
A Unified Kinetics and Equilibrium Experiment: Rate Law, Activation Energy, and Equilibrium Constant for the Dissociation of Ferroin Sattar, Simeen Journal of Chemical Education, Vol. 88, Issue 4 https://doi.org/10.1021/ed100797s	journal	January 2011
A Nickel Thiolate Catalyst for the Long-Lived Photocatalytic Production of Hydrogen in a Noble-Metal-Free System Han, Zhiji; McNamara, William R.; Eum, Min-Sik Angewandte Chemie International Edition, Vol. 51, Issue 7 https://doi.org/10.1002/anie.201107329	journal	January 2012
Dibenzo[a,e]cyclooctatetraene in a proposed test for heterogeneity in catalysts formed from soluble platinum-group metal complexes Anton, Douglas R.; Crabtree, Robert H. Organometallics, Vol. 2, Issue 7 https://doi.org/10.1021/om50001a013	journal	July 1983
Transformations in cobalt amalgam—from a homogeneous Co amalgam to nanocrystallites Paklepa, P.; Woroniecki, J.; Wrona, P. K. Journal of Electroanalytical Chemistry, Vol. 498, Issue 1-2 https://doi.org/10.1016/S0022-0728(00)00382-X	journal	February 2001
Palladium-catalyzed formation of carbon-nitrogen bonds. Reaction intermediates and catalyst improvements in the hetero cross-coupling of aryl halides and tin amides Paul, Frederic; Patt, Joe; Hartwig, John F. Journal of the American Chemical Society, Vol. 116, Issue 13 https://doi.org/10.1021/ja00092a058	journal	June 1994
Reduction potentials for 2,2'-bipyridine and 1,10-phenanthroline couples in aqueous solutions Krishnan, C. V.; Creutz, Carol; Schwarz, Harold A. Journal of the American Chemical Society, Vol. 105, Issue 17 https://doi.org/10.1021/ja00355a015	journal	August 1983
Excited State Redox Potentials of Ruthenium Diimine Complexes; Correlations with Ground State Redox Potentials and Ligand Parameters Vlcek, A. A.; Dodsworth, Elaine S.; Pietro, William J. Inorganic Chemistry, Vol. 34, Issue 7 https://doi.org/10.1021/ic00111a043	journal	March 1995
Some remarks about free radicals and the photochemistry of solutions Franck, J.; Rabinowitsch, E. Transactions of the Faraday Society, Vol. 30 https://doi.org/10.1039/tf9343000120	journal	January 1934
Electron Transfer and Alkyl Transfer with Cobaloximes in Aqueous Solutions. Kinetic Studies by Pulse Radiolysis Kumar, M.; Natarajan, E.; Neta, P. The Journal of Physical Chemistry, Vol. 98, Issue 33 https://doi.org/10.1021/j100084a018	journal	August 1994
Kinetic Studies of the Reduction of [Co(dmgH) ₂ (py)(Cl)] Revisited: Mechanisms, Products, and Implications Kahnt, Axel; Peuntinger, Katrin; Dammann, Claudia The Journal of Physical Chemistry A, Vol. 118, Issue 25 https://doi.org/10.1021/jp501947y	journal	June 2014

Cited By (1)

Mono and dinuclear iridium( iii ) complexes featuring bis-tridentate coordination and Schiff-base bridging ligands: the beneficial effect of a second metal ion on luminescence Puttock, Emma V.; Sil, Amit; Yufit, Dmitry S. Dalton Transactions, Vol. 49, Issue 30 https://doi.org/10.1039/d0dt01964j	journal	January 2020

Similar Records

Efficient Phosphorescence from Naphthalenebenzimidizole-Coordinated Iridium(III) Chromophores

Journal Article · 2017 · European Journal of Inorganic Chemistry · OSTI ID:1633624

Yarnell, James E.; De La Torre, Patricia; Castellano, Felix N.

Reactivity of radiolytically and photochemically generated tertiary amine radicals towards a CO₂ reduction catalyst

Journal Article · 2023 · Journal of Chemical Physics · OSTI ID:2222380

Carr, Cody R.; Vrionides, Michael A.; Grills, David C.

Understanding the Role of Inter- and Intramolecular Promoters in Electro- and Photochemical CO₂ Reduction Using Mn, Re, and Ru Catalysts

Journal Article · 2022 · Accounts of Chemical Research · OSTI ID:1858023

Fujita, Etsuko; Grills, David C.; Manbeck, Gerald F.; +1 more

Related Subjects

14 SOLAR ENERGY
solar fuels
photocatalysis
hydrogen production
electron transfer
iridium(III) photosensitizer
transient absorption spectroscopy

Title: A Robust Visible-Light-Harvesting Cyclometalated Ir(III) Diimine Sensitizer for Homogeneous Photocatalytic Hydrogen Production

Citation Formats

References (63)

Cited By (1)

Similar Records

Related Subjects