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

Abstract

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 (λex = 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 entermore » 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.« less

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
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  1. North Carolina State Univ., Raleigh, NC (United States)
Publication Date:
Research Org.:
North Carolina State University, Raleigh, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1633644
Grant/Contract Number:  
SC0011979
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Energy Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 2; Journal ID: ISSN 2574-0962
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; solar fuels; photocatalysis; hydrogen production; electron transfer; iridium(III) photosensitizer; transient absorption spectroscopy

Citation Formats

Yang, Mo, Yarnell, James E., El Roz, Karim, and Castellano, Felix N.. A Robust Visible-Light-Harvesting Cyclometalated Ir(III) Diimine Sensitizer for Homogeneous Photocatalytic Hydrogen Production. United States: N. p., 2020. Web. doi:10.1021/acsaem.9b02269.
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Yang, Mo, Yarnell, James E., El Roz, Karim, & Castellano, Felix N.. A Robust Visible-Light-Harvesting Cyclometalated Ir(III) Diimine Sensitizer for Homogeneous Photocatalytic Hydrogen Production. United States. https://doi.org/10.1021/acsaem.9b02269
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Yang, Mo, Yarnell, James E., El Roz, Karim, and Castellano, Felix N.. Mon . "A Robust Visible-Light-Harvesting Cyclometalated Ir(III) Diimine Sensitizer for Homogeneous Photocatalytic Hydrogen Production". United States. https://doi.org/10.1021/acsaem.9b02269. https://www.osti.gov/servlets/purl/1633644.
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@article{osti_1633644,
title = {A Robust Visible-Light-Harvesting Cyclometalated Ir(III) Diimine Sensitizer for Homogeneous Photocatalytic Hydrogen Production},
author = {Yang, Mo and Yarnell, James E. and El Roz, Karim and Castellano, Felix N.},
abstractNote = {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 (λex = 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.},
doi = {10.1021/acsaem.9b02269},
journal = {ACS Applied Energy Materials},
number = 2,
volume = 3,
place = {United States},
year = {2020},
month = {1}
}
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Works referenced in this record:

Solar fuels generation and molecular systems: is it homogeneous or heterogeneous catalysis?
journal, January 2013

  • Artero, Vincent; Fontecave, Marc
  • Chem. Soc. Rev., Vol. 42, Issue 6
  • DOI: 10.1039/C2CS35334B

Homogeneous Catalytic System for Photoinduced Hydrogen Production Utilizing Iridium and Rhodium Complexes
journal, November 2008

  • Cline, Eric D.; Adamson, Samantha E.; Bernhard, Stefan
  • Inorganic Chemistry, Vol. 47, Issue 22
  • DOI: 10.1021/ic800988b

[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
journal, November 2012

  • Stoll, Thibaut; Gennari, Marcello; Serrano, Isabel
  • Chemistry - A European Journal, Vol. 19, Issue 2
  • DOI: 10.1002/chem.201202555

Visible Light-Driven Electron Transfer and Hydrogen Generation Catalyzed by Bioinspired [2Fe2S] Complexes
journal, April 2008

  • Na, Yong; Wang, Mei; Pan, Jingxi
  • Inorganic Chemistry, Vol. 47, Issue 7
  • DOI: 10.1021/ic702010w

Homogeneous Photocatalytic H 2 Production Using a Ru II Bathophenanthroline Metal‐to‐Ligand Charge‐Transfer Photosensitizer
journal, October 2016

  • Khnayzer, Rony S.; Olaiya, Babatunde S.; El Roz, Karim A.
  • ChemPlusChem, Vol. 81, Issue 10
  • DOI: 10.1002/cplu.201600227

Discovery and High-Throughput Screening of Heteroleptic Iridium Complexes for Photoinduced Hydrogen Production
journal, May 2005

  • Goldsmith, Jonas I.; Hudson, William R.; Lowry, Michael S.
  • Journal of the American Chemical Society, Vol. 127, Issue 20
  • DOI: 10.1021/ja0427101

Photocatalytic H2 Production with a Rhenium/Cobalt System in Water under Acidic Conditions
journal, November 2011

  • Guttentag, Miguel; Rodenberg, Alexander; Kopelent, René
  • European Journal of Inorganic Chemistry, Vol. 2012, Issue 1
  • DOI: 10.1002/ejic.201100883

Robust Cuprous Phenanthroline Sensitizer for Solar Hydrogen Photocatalysis
journal, September 2013

  • Khnayzer, Rony S.; McCusker, Catherine E.; Olaiya, Babatunde S.
  • Journal of the American Chemical Society, Vol. 135, Issue 38
  • DOI: 10.1021/ja407816f

Ultrafast Excited-State Dynamics of Copper(I) Complexes
journal, February 2015

  • Iwamura, Munetaka; Takeuchi, Satoshi; Tahara, Tahei
  • Accounts of Chemical Research, Vol. 48, Issue 3
  • DOI: 10.1021/ar500353h

Transient Absorption Dynamics of Sterically Congested Cu(I) MLCT Excited States
journal, March 2015

  • Garakyaraghi, Sofia; Danilov, Evgeny O.; McCusker, Catherine E.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 13
  • DOI: 10.1021/acs.jpca.5b00901

Enhancing the Visible-Light Absorption and Excited-State Properties of Cu(I) MLCT Excited States
journal, February 2018

Ultrafast dynamics of ligand-field excited states
journal, July 2006

  • Juban, Eric A.; Smeigh, Amanda L.; Monat, Jeremy E.
  • Coordination Chemistry Reviews, Vol. 250, Issue 13-14
  • DOI: 10.1016/j.ccr.2006.02.010

Photochemical production of hydrogen and oxygen from water: A review and state of the art
journal, January 1995

Photochemical production of hydrogen from water
journal, May 1985

Homogeneous catalysis of platinum(II) complexes in photochemical hydrogen production from water
journal, November 2007

Visible Light Induced Catalytic Water Reduction without an Electron Relay
journal, October 2007

  • Tinker, Leonard L.; McDaniel, Neal D.; Curtin, Peter N.
  • Chemistry - A European Journal, Vol. 13, Issue 31
  • DOI: 10.1002/chem.200700480

Orchestrated Photocatalytic Water Reduction Using Surface-Adsorbing Iridium Photosensitizers
journal, August 2011

  • DiSalle, Brian F.; Bernhard, Stefan
  • Journal of the American Chemical Society, Vol. 133, Issue 31
  • DOI: 10.1021/ja201514e

Photon-Driven Catalytic Proton Reduction with a Robust Homoleptic Iridium(III) 6-Phenyl-2,2′-bipyridine Complex ([Ir(C /\ N /\ N) 2 ] + )
journal, November 2009

  • Tinker, Leonard L.; Bernhard, Stefan
  • Inorganic Chemistry, Vol. 48, Issue 22
  • DOI: 10.1021/ic900777g

Structure−Activity Correlations Among Iridium(III) Photosensitizers in a Robust Water-Reducing System
journal, July 2009

  • Curtin, Peter N.; Tinker, Leonard L.; Burgess, Christine M.
  • Inorganic Chemistry, Vol. 48, Issue 22
  • DOI: 10.1021/ic9007763

Highly Efficient Photocatalytic Water Reduction with Robust Iridium(III) Photosensitizers Containing Arylsilyl Substituents
journal, September 2013

  • Whang, Dong Ryeol; Sakai, Ken; Park, Soo Young
  • Angewandte Chemie International Edition, Vol. 52, Issue 44
  • DOI: 10.1002/anie.201305684

[Ir(N^N^N)(C^N)L] + : A New Family of Luminophores Combining Tunability and Enhanced Photostability
journal, January 2014

  • Chirdon, Danielle N.; Transue, Wesley J.; Kagalwala, Husain N.
  • Inorganic Chemistry, Vol. 53, Issue 3
  • DOI: 10.1021/ic402411g

Metal-complex chromophores for solar hydrogen generation
journal, January 2017

  • Yuan, Yong-Jun; Yu, Zhen-Tao; Chen, Da-Qin
  • Chemical Society Reviews, Vol. 46, Issue 3
  • DOI: 10.1039/C6CS00436A

Tricyclometalated Iridium Complexes as Highly Stable Photosensitizers for Light-Induced Hydrogen Evolution
journal, March 2013

  • Yuan, Yong-Jun; Yu, Zhen-Tao; Gao, Hong-Lin
  • Chemistry - A European Journal, Vol. 19, Issue 20
  • DOI: 10.1002/chem.201300146

Charge-Neutral Amidinate-Containing Iridium Complexes Capable of Efficient Photocatalytic Water Reduction
journal, November 2012

  • Yu, Zhen-Tao; Yuan, Yong-Jun; Cai, Jian-Guang
  • Chemistry - A European Journal, Vol. 19, Issue 4
  • DOI: 10.1002/chem.201203029

Synthetically Tailored Excited States: Phosphorescent, Cyclometalated Iridium(III) Complexes and Their Applications
journal, October 2006

  • Lowry, Michael S.; Bernhard, Stefan
  • Chemistry - A European Journal, Vol. 12, Issue 31
  • DOI: 10.1002/chem.200600618

Effect of ligand substituents of the d-d luminescence of iridium(III) and rhodium(III) complexes of 1,10-phenanthroline
journal, June 1974

  • Watts, Richard J.; Van Houten, J.
  • Journal of the American Chemical Society, Vol. 96, Issue 13
  • DOI: 10.1021/ja00820a053

Tracking of Tuning Effects in Bis-Cyclometalated Iridium Complexes: A Combined Time Resolved Infrared Spectroscopy, Electrochemical, and Computational Study
journal, July 2013

  • Chirdon, Danielle N.; McCusker, Catherine E.; Castellano, Felix N.
  • Inorganic Chemistry, Vol. 52, Issue 15
  • DOI: 10.1021/ic401009q

Cationic Bis-cyclometalated Iridium(III) Diimine Complexes and Their Use in Efficient Blue, Green, and Red Electroluminescent Devices
journal, November 2005

  • Tamayo, Arnold B.; Garon, Simona; Sajoto, Tissa
  • Inorganic Chemistry, Vol. 44, Issue 24
  • DOI: 10.1021/ic050970t

Photodriven Electron and Energy Transfer from Copper Phenanthroline Excited States
journal, January 1996

  • Ruthkosky, Mark; Castellano, Felix N.; Meyer, Gerald J.
  • Inorganic Chemistry, Vol. 35, Issue 22
  • DOI: 10.1021/ic960503z

Photoreduction of benzo-1,4-quinone sensitised by metalloporphyrins
journal, January 1983

  • Harriman, Anthony; Porter, George; Wilowska, Aleksandra
  • Journal of the Chemical Society, Faraday Transactions 2, Vol. 79, Issue 6
  • DOI: 10.1039/f29837900807

Visible Light-Driven Hydrogen Production from Aqueous Protons Catalyzed by Molecular Cobaloxime Catalysts
journal, June 2009

  • Du, Pingwu; Schneider, Jacob; Luo, Genggeng
  • Inorganic Chemistry, Vol. 48, Issue 11
  • DOI: 10.1021/ic900389z

A Homogeneous System for the Photogeneration of Hydrogen from Water Based on a Platinum(II) Terpyridyl Acetylide Chromophore and a Molecular Cobalt Catalyst
journal, September 2008

  • Du, Pingwu; Knowles, Kathryn; Eisenberg, Richard
  • Journal of the American Chemical Society, Vol. 130, Issue 38
  • DOI: 10.1021/ja804650g

Proton Electroreduction Catalyzed by Cobaloximes:  Functional Models for Hydrogenases
journal, June 2005

  • Razavet, Mathieu; Artero, Vincent; Fontecave, Marc
  • Inorganic Chemistry, Vol. 44, Issue 13
  • DOI: 10.1021/ic050167z

Homogeneous Photocatalytic Hydrogen Production Using π-Conjugated Platinum(II) Arylacetylide Sensitizers
journal, February 2011

  • Wang, Xianghuai; Goeb, Sébastien; Ji, Zhiqiang
  • Inorganic Chemistry, Vol. 50, Issue 3
  • DOI: 10.1021/ic101731j

The electro-oxidation of N,N-dimethyl-p-toluidine in acetonitrile:
journal, August 2002

  • Rees, Neil V.; Klymenko, Oleksiy V.; Compton, Richard G.
  • Journal of Electroanalytical Chemistry, Vol. 531, Issue 1
  • DOI: 10.1016/S0022-0728(02)01054-9

Efficient Phosphorescence from Naphthalenebenzimidizole‐Coordinated Iridium(III) Chromophores
journal, September 2017

  • Yarnell, James E.; De La Torre, Patricia; Castellano, Felix N.
  • European Journal of Inorganic Chemistry, Vol. 2017, Issue 44
  • DOI: 10.1002/ejic.201700669

Parallelization of photocatalytic gas-producing reactions
journal, March 2015

  • Khnayzer, Rony S.; Martin, Douglas R.; Codding, Charles L.
  • Review of Scientific Instruments, Vol. 86, Issue 3
  • DOI: 10.1063/1.4915349

Reductive quenching of ruthenium polypyridyl sensitizers by cyanometalate complexes
journal, September 1989

  • Mallouk, Thomas E.; Krueger, Jonathan S.; Mayer, James E.
  • Inorganic Chemistry, Vol. 28, Issue 18
  • DOI: 10.1021/ic00317a023

Homogeneous catalysis of the photoreduction of water by visible light. 2. Mediation by a tris(2,2'-bipyridine)ruthenium(II)-cobalt(II) bipyridine system
journal, April 1981

  • Krishnan, C. V.; Sutin, Norman
  • Journal of the American Chemical Society, Vol. 103, Issue 8
  • DOI: 10.1021/ja00398a066

Synthesis and Photophysical Characterizations of Thermal -Stable Naphthalene Benzimidazoles
journal, January 2011

Cyclometalated Iridium(III) Imidazole Phenanthroline Complexes as Luminescent and Electrochemiluminescent G-Quadruplex DNA Binders
journal, June 2015

1,10-Phenanthrolines: versatile building blocks for luminescent molecules, materials and metal complexes
journal, January 2009

  • Accorsi, Gianluca; Listorti, Andrea; Yoosaf, K.
  • Chemical Society Reviews, Vol. 38, Issue 6
  • DOI: 10.1039/b806408n

Synthesis and Characterization of Facial and Meridional Tris-cyclometalated Iridium(III) Complexes
journal, June 2003

  • Tamayo, Arnold B.; Alleyne, Bert D.; Djurovich, Peter I.
  • Journal of the American Chemical Society, Vol. 125, Issue 24
  • DOI: 10.1021/ja034537z

Emission and absorption of Ir(ppy)2(CO)(Cl) – temperature dependence, phosphorescence decay dynamics, and assignment of excited states
journal, October 2004

Highly Phosphorescent Bis-Cyclometalated Iridium Complexes:  Synthesis, Photophysical Characterization, and Use in Organic Light Emitting Diodes
journal, May 2001

  • Lamansky, Sergey; Djurovich, Peter; Murphy, Drew
  • Journal of the American Chemical Society, Vol. 123, Issue 18
  • DOI: 10.1021/ja003693s

Reductive Side of Water Splitting in Artificial Photosynthesis: New Homogeneous Photosystems of Great Activity and Mechanistic Insight
journal, November 2010

  • McCormick, Theresa M.; Calitree, Brandon D.; Orchard, Alexandra
  • Journal of the American Chemical Society, Vol. 132, Issue 44
  • DOI: 10.1021/ja1057357

Photocatalytic H 2 Production from Water with Rhenium and Cobalt Complexes
journal, April 2011

  • Probst, Benjamin; Guttentag, Miguel; Rodenberg, Alexander
  • Inorganic Chemistry, Vol. 50, Issue 8
  • DOI: 10.1021/ic102317u

Impact of Ligand Exchange in Hydrogen Production from Cobaloxime-Containing Photocatalytic Systems
journal, November 2011

  • McCormick, Theresa M.; Han, Zhiji; Weinberg, David J.
  • Inorganic Chemistry, Vol. 50, Issue 21
  • DOI: 10.1021/ic2010166

A Nickel Thiolate Catalyst for the Long-Lived Photocatalytic Production of Hydrogen in a Noble-Metal-Free System
journal, January 2012

  • Han, Zhiji; McNamara, William R.; Eum, Min-Sik
  • Angewandte Chemie International Edition, Vol. 51, Issue 7
  • DOI: 10.1002/anie.201107329

Dibenzo[a,e]cyclooctatetraene in a proposed test for heterogeneity in catalysts formed from soluble platinum-group metal complexes
journal, July 1983

  • Anton, Douglas R.; Crabtree, Robert H.
  • Organometallics, Vol. 2, Issue 7
  • DOI: 10.1021/om50001a013

Transformations in cobalt amalgam—from a homogeneous Co amalgam to nanocrystallites
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
journal, June 1994

  • Paul, Frederic; Patt, Joe; Hartwig, John F.
  • Journal of the American Chemical Society, Vol. 116, Issue 13
  • DOI: 10.1021/ja00092a058

Reduction potentials for 2,2'-bipyridine and 1,10-phenanthroline couples in aqueous solutions
journal, August 1983

  • Krishnan, C. V.; Creutz, Carol; Schwarz, Harold A.
  • Journal of the American Chemical Society, Vol. 105, Issue 17
  • DOI: 10.1021/ja00355a015

Excited State Redox Potentials of Ruthenium Diimine Complexes; Correlations with Ground State Redox Potentials and Ligand Parameters
journal, March 1995

  • Vlcek, A. A.; Dodsworth, Elaine S.; Pietro, William J.
  • Inorganic Chemistry, Vol. 34, Issue 7
  • DOI: 10.1021/ic00111a043

Some remarks about free radicals and the photochemistry of solutions
journal, January 1934

  • Franck, J.; Rabinowitsch, E.
  • Transactions of the Faraday Society, Vol. 30
  • DOI: 10.1039/tf9343000120

Electron Transfer and Alkyl Transfer with Cobaloximes in Aqueous Solutions. Kinetic Studies by Pulse Radiolysis
journal, August 1994

  • Kumar, M.; Natarajan, E.; Neta, P.
  • The Journal of Physical Chemistry, Vol. 98, Issue 33
  • DOI: 10.1021/j100084a018

Kinetic Studies of the Reduction of [Co(dmgH) 2 (py)(Cl)] Revisited: Mechanisms, Products, and Implications
journal, June 2014

  • Kahnt, Axel; Peuntinger, Katrin; Dammann, Claudia
  • The Journal of Physical Chemistry A, Vol. 118, Issue 25
  • DOI: 10.1021/jp501947y
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