New Rh2 (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity

Whittemore, Tyler J.; Sayre, Hannah J.; Xue, Congcong; White, Travis A.; Gallucci, Judith C.; Turro, Claudia

doi:10.1021/jacs.7b08489

Title: New Rh₂ (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity

Journal Article · Wed Oct 04 00:00:00 EDT 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b08489· OSTI ID:1430209

Whittemore, Tyler J. ^[1]; Sayre, Hannah J. ^[1]; Xue, Congcong ^[1];

^[1]; Gallucci, Judith C. ^[1];

^[1]

The Ohio State Univ., Columbus, OH (United States). Department of Chemistry and Biochemistry

In this work, the new heteroleptic paddlewheel complexes cis-[Rh₂(μ-form)₂(μ-np)₂][BF₄]₂, where form = p-ditolylformamidinate (DTolF) or p-difluorobenzylformamidinate (F-form) and np = 1,8-napthyridyine, and cis-Rh₂(μ-form)₂(μ-npCOO)₂ (npCOO^– = 1,8-naphthyridine-2-carboxylate), were synthesized and characterized. The complexes absorb strongly throughout the ultraviolet (λ_max = 300 nm, ε = 20 300 M^–1 cm^–1) and visible regions (λ_max = 640 nm ε = 3500 M^–1 cm^–1), making them potentially useful new dyes with panchromatic light absorption for solar energy conversion applications. Ultrafast and nanosecond transient absorption and time-resolved infrared spectroscopies were used to characterize the identity and dynamics of the excited states, where singlet and triplet Rh₂/form-to-naphthyridine, metal/ligand-to-ligand charge-transfer (ML-LCT) excited states were observed in all four complexes. The npCOO^– complexes exhibit red-shifted absorption profiles extending into the near-IR and undergo photoinitiated electron transfer to generate reduced methyl viologen, a species that persists in the presence of a sacrificial donor. The energy of the triplet excited state of each complex was estimated from energy-transfer quenching experiments using a series of organic triplet donors (E(³ππ*) from 1.83 to 0.78 eV). The singlet reduction (+0.6 V vs Ag/AgCl) potentials, and singlet and triplet oxidation potentials (-1.1 and -0.5 V vs Ag/AgCl, respectively) were determined. Finally, based on the excited-state lifetimes and redox properties, these complexes represent a new class of light absorbers with potential application as dyes for charge injection into semiconductor solar cells and in sensitizer-catalyst assemblies for photocatalysis that operate with irradiation from the ultraviolet to ~800 nm.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: The Ohio State Univ., Columbus, OH (United States)

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

Grant/Contract Number:: SC0010542

OSTI ID:: 1430209

Journal Information:: Journal of the American Chemical Society, Vol. 139, Issue 41; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 28 works

Citation information provided by
Web of Science

References (48)

Solar radiation and human health Moan, Johan; Juzeniene, Asta Journal of Photochemistry and Photobiology B: Biology, Vol. 101, Issue 2 https://doi.org/10.1016/j.jphotobiol.2010.08.004	journal	November 2010
Finding the Way to Solar Fuels with Dye-Sensitized Photoelectrosynthesis Cells Brennaman, M. Kyle; Dillon, Robert J.; Alibabaei, Leila Journal of the American Chemical Society, Vol. 138, Issue 40 https://doi.org/10.1021/jacs.6b06466	journal	September 2016
Dye-Sensitized Solar Cells Hagfeldt, Anders; Boschloo, Gerrit; Sun, Licheng Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr900356p	journal	November 2010
Optimizing Dyes for Dye-Sensitized Solar Cells Robertson, Neil Angewandte Chemie International Edition, Vol. 45, Issue 15 https://doi.org/10.1002/anie.200503083	journal	April 2006
Influence of Ancillary Ligands in Dye-Sensitized Solar Cells Pashaei, Babak; Shahroosvand, Hashem; Graetzel, Michael Chemical Reviews, Vol. 116, Issue 16 https://doi.org/10.1021/acs.chemrev.5b00621	journal	August 2016
Wireless Solar Water Splitting Using Silicon-Based Semiconductors and Earth-Abundant Catalysts Reece, S. Y.; Hamel, J. A.; Sung, K. Science, Vol. 334, Issue 6056 https://doi.org/10.1126/science.1209816	journal	September 2011
Accumulative Charge Separation for Solar Fuels Production: Coupling Light-Induced Single Electron Transfer to Multielectron Catalysis Hammarström, Leif Accounts of Chemical Research, Vol. 48, Issue 3 https://doi.org/10.1021/ar500386x	journal	February 2015
Conversion of light to electricity by cis-X₂bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) charge-transfer sensitizers (X = Cl^-, Br^-, I^-, CN^-, and SCN^-) on nanocrystalline titanium dioxide electrodes Nazeeruddin, M. K.; Kay, A.; Rodicio, I. Journal of the American Chemical Society, Vol. 115, Issue 14, p. 6382-6390 https://doi.org/10.1021/ja00067a063	journal	July 1993
Squaraine-sensitized composite of a reduced graphene oxide/TiO ₂ photocatalyst: π–π stacking as a new method of dye anchoring Joseph, K. L. Vincent; Lim, Jonghun; Anthonysamy, A. Journal of Materials Chemistry A, Vol. 3, Issue 1 https://doi.org/10.1039/C4TA04313H	journal	January 2015
Near-infrared squaraine co-sensitizer for high-efficiency dye-sensitized solar cells Rao, G. Hanumantha; Venkateswararao, A.; Giribabu, L. Physical Chemistry Chemical Physics, Vol. 18, Issue 21 https://doi.org/10.1039/C6CP01669C	journal	January 2016
Porphyrin-sensitized solar cells Li, Lu-Lin; Diau, Eric Wei-Guang Chem. Soc. Rev., Vol. 42, Issue 1 https://doi.org/10.1039/C2CS35257E	journal	January 2013
Highly efficient porphyrin-sensitized solar cells with enhanced light harvesting ability beyond 800 nm and efficiency exceeding 10% Wang, Chin-Li; Hu, Jyun-Yu; Wu, Cheng-Hua Energy & Environmental Science, Vol. 7, Issue 4 https://doi.org/10.1039/c3ee44168g	journal	January 2014
Porphyrin Cosensitization for a Photovoltaic Efficiency of 11.5%: A Record for Non-Ruthenium Solar Cells Based on Iodine Electrolyte Xie, Yongshu; Tang, Yunyu; Wu, Wenjun Journal of the American Chemical Society, Vol. 137, Issue 44 https://doi.org/10.1021/jacs.5b09665	journal	October 2015
Molecular Engineering of Phthalocyanine Sensitizers for Dye-Sensitized Solar Cells Ince, Mine; Yum, Jun-Ho; Kim, Yongjoo The Journal of Physical Chemistry C, Vol. 118, Issue 30 https://doi.org/10.1021/jp502447y	journal	April 2014
Design of an Organic Chromophore for P-Type Dye-Sensitized Solar Cells Qin, Peng; Zhu, Hongjun; Edvinsson, Tomas Journal of the American Chemical Society, Vol. 130, Issue 27 https://doi.org/10.1021/ja8001474	journal	July 2008
Cyclometalated Ruthenium Sensitizers Bearing a Triphenylamino Group for p-Type NiO Dye-Sensitized Solar Cells Ji, Zhiqiang; Natu, Gaytri; Wu, Yiying ACS Applied Materials & Interfaces, Vol. 5, Issue 17 https://doi.org/10.1021/am402263q	journal	August 2013
Photophysical Properties of MM Quadruply Bonded Complexes Supported by Carboxylate Ligands, MM = Mo ₂ , MoW, or W ₂ Chisholm, Malcolm H.; Gustafson, Terry L.; Turro, Claudia Accounts of Chemical Research, Vol. 46, Issue 2 https://doi.org/10.1021/ar3002206	journal	November 2012
Directional charge transfer and highly reducing and oxidizing excited states of new dirhodium( ii , ii ) complexes: potential applications in solar energy conversion Li, Zhanyong; Leed, Nicholas A.; Dickson-Karn, Nicole M. Chem. Sci., Vol. 5, Issue 2 https://doi.org/10.1039/C3SC52366G	journal	January 2014
Photophysical Properties of cis -Mo ₂ Quadruply Bonded Complexes and Observation of Photoinduced Electron Transfer to Titanium Dioxide Brown-Xu, Samantha E.; Chisholm, Malcolm H.; Durr, Christopher B. Journal of the American Chemical Society, Vol. 136, Issue 32 https://doi.org/10.1021/ja504944d	journal	July 2014
Electronic influences of bridging and chelating diimine ligand coordination in formamidinate-bridged Rh2(II,II) dimers White, Travis A.; Dunbar, Kim R.; Thummel, Randolph P. Polyhedron, Vol. 103 https://doi.org/10.1016/j.poly.2015.10.015	journal	January 2016
A Novel Dirhodium Compound with Neutral, Bridging 9-Ethyladenine Ligands Catalan, Kemal V.; Mindiola, Daniel J.; Ward, Donald L. Inorganic Chemistry, Vol. 36, Issue 11 https://doi.org/10.1021/ic960682k	journal	May 1997
NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist Fulmer, Gregory R.; Miller, Alexander J. M.; Sherden, Nathaniel H. Organometallics, Vol. 29, Issue 9 https://doi.org/10.1021/om100106e	journal	May 2010
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015
Excited-State Properties of Rh ₂ (O ₂ CCH ₃ ) ₄ (L) ₂ (L = CH ₃ OH, THF, PPh ₃ , py) Bradley, Patricia M.; Bursten, Bruce E.; Turro, Claudia Inorganic Chemistry, Vol. 40, Issue 6 https://doi.org/10.1021/ic0009573	journal	March 2001
Early Events in the Photochemistry of Aryl Azides from Femtosecond UV/Vis Spectroscopy and Quantum Chemical Calculations Burdzinski, Gotard; Hackett, John C.; Wang, Jin Journal of the American Chemical Society, Vol. 128, Issue 41 https://doi.org/10.1021/ja061520i	journal	October 2006
Ultrafast Carbene−Carbene Isomerization Wang, Jin; Burdzinski, Gotard; Kubicki, Jacek Journal of the American Chemical Society, Vol. 130, Issue 16 https://doi.org/10.1021/ja8002827	journal	March 2008
Electronic structure and spectra of ruthenium diimine complexes by density functional theory and INDO/S. Comparison of the two methods Gorelsky, S. I.; Lever, A. B. P. Journal of Organometallic Chemistry, Vol. 635, Issue 1-2 https://doi.org/10.1016/S0022-328X(01)01079-8	journal	October 2001
Multiple Bonds between Metal Atoms. 3rd Edition Edited by F. Albert Cotton, Carlos A. Murillo and Richard A. Walton. Kauffman, George B. Angewandte Chemie International Edition, Vol. 46, Issue 15 https://doi.org/10.1002/anie.200585495	journal	April 2007
Synthesis and characterization of dirhodium(II,II) formamidinate complexes containing short-bite nitrogen ligands Tresoldi, Giuseppe; Lo Schiavo, Sandra; Nicolò, Francesco Inorganica Chimica Acta, Vol. 344 https://doi.org/10.1016/S0020-1693(02)01303-8	journal	February 2003
Electronic structure of phosphine adducts of tetrakis(carboxylato) dirhodium(II). Pronounced influence of axial ligands Bursten, Bruce E.; Cotton, F. Albert Inorganic Chemistry, Vol. 20, Issue 9 https://doi.org/10.1021/ic50223a056	journal	September 1981
Electronic structure of the rhodium-rhodium bond in dirhodium tetracarboxylates by a study of electronic spectra of neutral molecules and their cation radicals Sowa, Takayoshi; Kawamura, Takashi; Shida, Tadamasa Inorganic Chemistry, Vol. 22, Issue 1 https://doi.org/10.1021/ic00143a014	journal	January 1983
Metal-metal bond in binuclear rhodium(II) acetate monohydrate Dubicki, L.; Martin, Raymond Leslie Inorganic Chemistry, Vol. 9, Issue 3 https://doi.org/10.1021/ic50085a049	journal	March 1970
A combined magnetic circular dichroism and density functional theory approach for the elucidation of electronic structure and bonding in three- and four-coordinate iron( ii )–N-heterocyclic carbene complexes Fillman, Kathlyn L.; Przyojski, Jacob A.; Al-Afyouni, Malik H. Chemical Science, Vol. 6, Issue 2 https://doi.org/10.1039/C4SC02791D	journal	January 2015
The Mayer bond order as a tool in inorganic chemistry† Bridgeman, Adam J.; Cavigliasso, Germán; Ireland, Luke R. Journal of the Chemical Society, Dalton Transactions, Issue 14 https://doi.org/10.1039/b102094n	journal	January 2001
Ultrafast Fluorescence Detection in Tris(2,2‘-bipyridine)ruthenium(II) Complex in Solution: Relaxation Dynamics Involving Higher Excited States Bhasikuttan, Achikanath C.; Suzuki, Masaya; Nakashima, Satoru Journal of the American Chemical Society, Vol. 124, Issue 28 https://doi.org/10.1021/ja026135h	journal	July 2002
Intersystem crossing in transition metal complexes Forster, Leslie S. Coordination Chemistry Reviews, Vol. 250, Issue 15-16 https://doi.org/10.1016/j.ccr.2006.01.023	journal	August 2006
Photoinduced charge separation and recombination kinetics in a dimeric iridium(I) complex with covalently bound alkyl-pyridinium acceptors Fox, Lucius S.; Marshall, Janet L.; Gray, Harry B. Journal of the American Chemical Society, Vol. 109, Issue 22 https://doi.org/10.1021/ja00256a081	journal	October 1987
Structural Control of ¹ A _2u -to- ³ A _2u Intersystem Crossing in Diplatinum(II,II) Complexes Durrell, Alec C.; Keller, Gretchen E.; Lam, Yan-Choi Journal of the American Chemical Society, Vol. 134, Issue 34 https://doi.org/10.1021/ja305666b	journal	August 2012
Excited-state decay processes of binuclear rhodium(I) isocyanide complexes Miskowski, Vincent M.; Rice, Steven F.; Gray, Harry B. The Journal of Physical Chemistry, Vol. 97, Issue 17 https://doi.org/10.1021/j100119a007	journal	April 1993
Detection of the Singlet and Triplet MM δδ* States in Quadruply Bonded Dimetal Tetracarboxylates (M = Mo, W) by Time-Resolved Infrared Spectroscopy Alberding, Brian G.; Chisholm, Malcolm H.; Gustafson, Terry L. Inorganic Chemistry, Vol. 51, Issue 1 https://doi.org/10.1021/ic201957a	journal	November 2011
Vibrational coherence in the excited state dynamics of Cr(acac)3: probing the reaction coordinate for ultrafast intersystem crossing Schrauben, Joel N.; Dillman, Kevin L.; Beck, Warren F. Chemical Science, Vol. 1, Issue 3 https://doi.org/10.1039/c0sc00262c	journal	January 2010
Investigating interfacial electron transfer in dye-sensitized NiO using vibrational spectroscopy Black, Fiona A.; Clark, Charlotte A.; Summers, Gareth H. Physical Chemistry Chemical Physics, Vol. 19, Issue 11 https://doi.org/10.1039/C6CP05712H	journal	January 2017
The absolute energy positions of conduction and valence bands of selected semiconducting minerals Xu, Yong; Schoonen, Martin A. A. American Mineralogist, Vol. 85, Issue 3-4 https://doi.org/10.2138/am-2000-0416	journal	March 2000
Photoinduced hole injection in semiconductor-coordination compound systems Buchalska, Marta; Kuncewicz, Joanna; Świętek, Elżbieta Coordination Chemistry Reviews, Vol. 257, Issue 3-4 https://doi.org/10.1016/j.ccr.2012.09.017	journal	February 2013
Electron injection dynamics in dye-sensitized semiconductor nanocrystalline films Furube, Akihiro; Katoh, Ryuzi; Hara, Kohjiro Surface Science Reports, Vol. 69, Issue 4 https://doi.org/10.1016/j.surfrep.2014.09.003	journal	December 2014
New Photovoltaic Devices Based on the Sensitization of p-type Semiconductors: Challenges and Opportunities Odobel, Fabrice; Le Pleux, Loïc; Pellegrin, Yann Accounts of Chemical Research, Vol. 43, Issue 8 https://doi.org/10.1021/ar900275b	journal	August 2010
Electrochemistry of the viologens Bird, C. L.; Kuhn, A. T. Chemical Society Reviews, Vol. 10, Issue 1 https://doi.org/10.1039/cs9811000049	journal	January 1981
Excited State Dynamics of Methyl Viologen. Ultrafast Photoreduction in Methanol and Fluorescence in Acetonitrile Peon, Jorge; Tan, Xin; Hoerner, J. David The Journal of Physical Chemistry A, Vol. 105, Issue 24 https://doi.org/10.1021/jp010084d	journal	June 2001

Cited By (5)

Photocatalytic H ₂ production by dirhodium( ii , ii ) photosensitizers with red light Sayre, Hannah J.; Millet, Agustin; Dunbar, Kim R. Chemical Communications, Vol. 54, Issue 60 https://doi.org/10.1039/c8cc03631d	journal	January 2018
Unbridged Rh( ii )–Rh( ii ) complexes of N-heterocyclic carbenes and reactions with O ₂ to form dirhodium( μ – η ¹ : η ¹ -O ₂ ) complexes Yi, Xiaofei; Liu, Bin; Chen, Kai Dalton Transactions, Vol. 48, Issue 12 https://doi.org/10.1039/c9dt00421a	journal	January 2019
One-step synthesis of ball-shaped metal complexes with a main absorption band in the near-IR region Furuyama, Taniyuki; Shimasaki, Fumika; Saikawa, Natsumi Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-53014-7	journal	November 2019
Two Four‐Coordinate and Seven‐Coordinate Co ^II Complexes Based on the Bidentate Ligand 1, 8‐Naphthyridine Showing Slow Magnetic Relaxation Behavior Huang, Xing‐Cai; Xu, Rui; Chen, Yong‐Zhi Chemistry – An Asian Journal, Vol. 15, Issue 2 https://doi.org/10.1002/asia.201901395	journal	December 2019
Electron injection into titanium dioxide by panchromatic dirhodium photosensitizers with low energy red light Xue, Congcong; Sayre, Hannah J.; Turro, Claudia Chemical Communications, Vol. 55, Issue 70 https://doi.org/10.1039/c9cc04677a	journal	January 2019

Figures / Tables (8)

Similar Records

Tunable Rh₂(II,II) Light Absorbers as Excited State Electron Donors and Acceptors Accessible with Red/Near-IR Irradiation

Journal Article · Wed Apr 04 00:00:00 EDT 2018 · Journal of the American Chemical Society · OSTI ID:1430209

Whittemore, Tyler; Millet, Agustin; Sayre, Hannah; +5 more

Electronic influences of bridging and chelating diimine ligand coordination in formamidinate-bridged Rh₂ (II,II) dimers

Journal Article · Thu Oct 22 00:00:00 EDT 2015 · Polyhedron · OSTI ID:1430209

White, Travis A.; Dunbar, Kim R.; Thummel, Randolph P.; +1 more

New Rh ₂ (II,II) Architecture for the Catalytic Reduction of H ⁺

Journal Article · Fri Sep 25 00:00:00 EDT 2015 · Inorganic Chemistry · OSTI ID:1430209

White, Travis A.; Witt, Suzanne E.; Li, Zhanyong; +2 more

Related Subjects

14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Dirhodium
naphthyridine
light absorption
time-resolved
excited state
infrared spectroscopy

Title: New Rh2 (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity

Citation Formats