Bathochromic Shifts in Rhenium Carbonyl Dyes Induced through Destabilization of Occupied Orbitals
Abstract
A series of rhenium diimine carbonyl complexes was prepared and characterized in order to examine the influence of axial ligands on electronic structure. Systematic substitution of the axial carbonyl and acetonitrile ligands of [Re(deeb)(CO)3(NCCH3)]+ (deeb = 4,4'-diethylester-2,2'-bipyridine) with trimethylphosphine and chloride, respectively, gives rise to red-shifted absorbance features. These bathochromic shifts result from destabilization of the occupied d-orbitals involved in metal-to-ligand charge-transfer transitions. Finally, Time-Dependent Density Functional Theory identified the orbitals involved in each transition and provided support for the changes in orbital energies induced by ligand substitution.
- Authors:
-
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; National Univ. of Singapore (Singapore). Dept. of Chemistry
- Eckerd College, St. Petersburg, FL (United States). Dept. of Chemistry
- Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1470299
- Grant/Contract Number:
- SC0001011
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 57; Journal Issue: 9; Related Information: UNC partners with University of North Carolina (lead); Duke University; University of Florida; Georgia Institute of Technology; University; North Carolina Central University; Research Triangle Institute; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); solar (photovoltaic); solar (fuels); photosynthesis (natural and artificial); hydrogen and fuel cells; electrodes - solar; charge transport; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly)
Citation Formats
Kurtz, Daniel A., Brereton, Kelsey R., Ruoff, Kevin P., Tang, Hui Min, Felton, Greg A. N., Miller, Alexander J. M., and Dempsey, Jillian L. Bathochromic Shifts in Rhenium Carbonyl Dyes Induced through Destabilization of Occupied Orbitals. United States: N. p., 2018.
Web. doi:10.1021/acs.inorgchem.8b00360.
Kurtz, Daniel A., Brereton, Kelsey R., Ruoff, Kevin P., Tang, Hui Min, Felton, Greg A. N., Miller, Alexander J. M., & Dempsey, Jillian L. Bathochromic Shifts in Rhenium Carbonyl Dyes Induced through Destabilization of Occupied Orbitals. United States. https://doi.org/10.1021/acs.inorgchem.8b00360
Kurtz, Daniel A., Brereton, Kelsey R., Ruoff, Kevin P., Tang, Hui Min, Felton, Greg A. N., Miller, Alexander J. M., and Dempsey, Jillian L. Thu .
"Bathochromic Shifts in Rhenium Carbonyl Dyes Induced through Destabilization of Occupied Orbitals". United States. https://doi.org/10.1021/acs.inorgchem.8b00360. https://www.osti.gov/servlets/purl/1470299.
@article{osti_1470299,
title = {Bathochromic Shifts in Rhenium Carbonyl Dyes Induced through Destabilization of Occupied Orbitals},
author = {Kurtz, Daniel A. and Brereton, Kelsey R. and Ruoff, Kevin P. and Tang, Hui Min and Felton, Greg A. N. and Miller, Alexander J. M. and Dempsey, Jillian L.},
abstractNote = {A series of rhenium diimine carbonyl complexes was prepared and characterized in order to examine the influence of axial ligands on electronic structure. Systematic substitution of the axial carbonyl and acetonitrile ligands of [Re(deeb)(CO)3(NCCH3)]+ (deeb = 4,4'-diethylester-2,2'-bipyridine) with trimethylphosphine and chloride, respectively, gives rise to red-shifted absorbance features. These bathochromic shifts result from destabilization of the occupied d-orbitals involved in metal-to-ligand charge-transfer transitions. Finally, Time-Dependent Density Functional Theory identified the orbitals involved in each transition and provided support for the changes in orbital energies induced by ligand substitution.},
doi = {10.1021/acs.inorgchem.8b00360},
journal = {Inorganic Chemistry},
number = 9,
volume = 57,
place = {United States},
year = {Thu Apr 12 00:00:00 EDT 2018},
month = {Thu Apr 12 00:00:00 EDT 2018}
}
Web of Science
Works referenced in this record:
Efficient photocatalytic CO2 reduction using [Re(bpy) (CO)3{P(OEt)3}]+
journal, May 1996
- Hori, Hisao; Johnson, Frank P. A.; Koike, Kazuhide
- Journal of Photochemistry and Photobiology A: Chemistry, Vol. 96, Issue 1-3
Key Process of the Photocatalytic Reduction of CO 2 Using [Re(4,4‘-X 2 -bipyridine)(CO) 3 PR 3 ] + (X = CH 3 , H, CF 3 ; PR 3 = Phosphorus Ligands): Dark Reaction of the One-Electron-Reduced Complexes with CO 2
journal, December 1997
- Koike, Kazuhide; Hori, Hisao; Ishizuka, Masakazu
- Organometallics, Vol. 16, Issue 26
Photophysical Behavior of a New CO2 Reduction Catalyst, Re(CO)2(bpy){P(OEt)3}2+
journal, October 1994
- Ishitani, Osamu; George, Michael W.; Ibusuki, Takashi
- Inorganic Chemistry, Vol. 33, Issue 21
Selective H2 and CO production with rhenium(I) biscarbonyl complexes as photocatalyst
journal, June 2012
- Morimoto, Tatsuki; Tanabe, Junji; Sakamoto, Kazuhiko
- Research on Chemical Intermediates, Vol. 39, Issue 1
Tryptophan-Accelerated Electron Flow Through Proteins
journal, June 2008
- Shih, C.; Museth, A. K.; Abrahamsson, M.
- Science, Vol. 320, Issue 5884
Modulation of Y 356 Photooxidation in E. coli Class Ia Ribonucleotide Reductase by Y 731 Across the α 2 :β 2 Interface
journal, August 2013
- Pizano, Arturo A.; Olshansky, Lisa; Holder, Patrick G.
- Journal of the American Chemical Society, Vol. 135, Issue 36
Photo-ribonucleotide reductase 2 by selective cysteine labeling with a radical phototrigger
journal, December 2011
- Pizano, A. A.; Lutterman, D. A.; Holder, P. G.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 1
Charge-Transfer Dynamics at the α/β Subunit Interface of a Photochemical Ribonucleotide Reductase
journal, January 2016
- Olshansky, Lisa; Stubbe, JoAnne; Nocera, Daniel G.
- Journal of the American Chemical Society, Vol. 138, Issue 4
Proton-Coupled Electron Flow in Protein Redox Machines
journal, December 2010
- Dempsey, Jillian L.; Winkler, Jay R.; Gray, Harry B.
- Chemical Reviews, Vol. 110, Issue 12
Photosensitized generation of singlet oxygen from rhenium(i) and iridium(iii) complexes
journal, January 2007
- Abdel-Shafi, Ayman A.; Bourdelande, Jose L.; Ali, Sameh S.
- Dalton Transactions, Issue 24
Rhenium(i) tricarbonyl polypyridine complexes showing strong absorption of visible light and long-lived triplet excited states as a triplet photosensitizer for triplet–triplet annihilation upconversion
journal, January 2012
- Yi, Xiuyu; Zhao, Jianzhang; Wu, Wanhua
- Dalton Transactions, Vol. 41, Issue 29
Photophysics of metal-organic π-conjugated polymers
journal, April 1998
- Ley, K. D.; Schanze, K. S.
- Coordination Chemistry Reviews, Vol. 171
Rhenium complexes in homogeneous hydrogen evolution
journal, December 2015
- Zarkadoulas, Athanasios; Koutsouri, Eugenia; Kefalidi, Christina
- Coordination Chemistry Reviews, Vol. 304-305
Photophysical properties of polypyridyl carbonyl complexes of rhenium(I)
journal, January 1991
- Worl, Laura A.; Duesing, Rich; Chen, Pingyun
- Journal of the Chemical Society, Dalton Transactions, Issue S
Application of the energy gap law to nonradiative, excited-state decay
journal, March 1983
- Caspar, Jonathan V.; Meyer, Thomas J.
- The Journal of Physical Chemistry, Vol. 87, Issue 6
Are Re( i ) phenanthroline complexes suitable candidates for OLEDs? Answers from DFT and TD-DFT investigations
journal, January 2014
- Velmurugan, Gunasekaran; Ramamoorthi, Balajangamanahalli K.; Venuvanalingam, Ponnambalam
- Phys. Chem. Chem. Phys., Vol. 16, Issue 39
Diffusion-Limited Interfacial Electron Transfer with Large Apparent Driving Forces
journal, September 1999
- Hasselmann, Georg M.; Meyer, Gerald J.
- The Journal of Physical Chemistry B, Vol. 103, Issue 36
Sensitization of Nanocrystalline TiO 2 Initiated by Reductive Quenching of Molecular Excited States
journal, February 1999
- Thompson, David W.; Kelly, Craig A.; Farzad, Fereshteh
- Langmuir, Vol. 15, Issue 3
Photochemical Ligand Substitution Reactions of fac -[Re(bpy)(CO) 3 Cl] and Derivatives
journal, March 2007
- Sato, Shunsuke; Sekine, Akiko; Ohashi, Yuji
- Inorganic Chemistry, Vol. 46, Issue 9
New Synthetic Routes to Biscarbonylbipyridinerhenium(I) Complexes cis,trans -[Re(X 2 bpy)(CO) 2 (PR 3 )(Y)] n + (X 2 bpy = 4,4‘-X 2 -2,2‘-bipyridine) via Photochemical Ligand Substitution Reactions, and Their Photophysical and Electrochemical Properties
journal, June 2000
- Koike, Kazuhide; Tanabe, Junji; Toyama, Shigeki
- Inorganic Chemistry, Vol. 39, Issue 13
Non-photochemical synthesis of Re(diimine)(CO)2(L)Cl (L = phosphine or phosphite) compounds
journal, September 2015
- Kurtz, Daniel A.; Dhakal, Badrinath; Donovan, Elizabeth S.
- Inorganic Chemistry Communications, Vol. 59
Luminescent Rhenium(I) Phenanthroline Complexes with a Benzoxazol-2-ylidene Ligand: Synthesis, Characterization, and Photophysical Study
journal, October 2012
- Ko, Chi-Chiu; Ng, Chi-On; Yiu, Shek-Man
- Organometallics, Vol. 31, Issue 20
Dual Emission from Rhenium(I) Complexes Induced by an Interligand Aromatic Interaction
journal, February 2012
- Morimoto, Tatsuki; Ito, Megumi; Koike, Kazuhide
- Chemistry - A European Journal, Vol. 18, Issue 11
Preparative Routes to Luminescent Mixed-Ligand Rhenium(I) Dicarbonyl Complexes
journal, March 2006
- Smithback, Joanna L.; Helms, Jeffrey B.; Schutte, Erick
- Inorganic Chemistry, Vol. 45, Issue 5
Correlations between photophysical and electrochemical properties for a series of new Mn carbonyl complexes containing substituted phenanthroline ligands
journal, March 2015
- Kurtz, Daniel A.; Dhakal, Badrinath; Hulme, Richard J.
- Inorganica Chimica Acta, Vol. 427
The Luminescence Rigidochromic Effect Exhibited by Organometallic Complexes: Rationale and Applications
journal, November 1995
- Lees, Alistair J.
- Comments on Inorganic Chemistry, Vol. 17, Issue 6
Electronic structures and spectral properties of rhenium(I) tricarbonyl diimine complexes with phosphine ligands: DFT/TDDFT theoretical investigations
journal, April 2012
- Zhao, Feng; Wang, Jie-xiu; Liu, Wen-qu
- Computational and Theoretical Chemistry, Vol. 985
New dinuclear hydrido-carbonyl rhenium complexes designed as photosensitizers in dye-sensitized solar cells
journal, January 2016
- Veronese, Lorenzo; Procopio, Elsa Quartapelle; De Rossi, Francesca
- New Journal of Chemistry, Vol. 40, Issue 3
Medium effect on the equilibrium geometries, vibrational frequencies and solvation energies of sulfanilamide
journal, November 2010
- Halim, Mohammad A.; Shaw, Dawn M.; Poirier, Raymond A.
- Journal of Molecular Structure: THEOCHEM, Vol. 960, Issue 1-3
An Evaluation of Harmonic Vibrational Frequency Scale Factors
journal, November 2007
- Merrick, Jeffrey P.; Moran, Damian; Radom, Leo
- The Journal of Physical Chemistry A, Vol. 111, Issue 45
Electrochemical and mechanistic studies of Re(CO)3(dmbpy)CI] and their relation to the catalytic reduction of CO2
journal, April 1986
- Breikss, Anne I.; Abruña, Hector D.
- Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 201, Issue 2
Metallocene electrochemistry
journal, January 1980
- Gale, R. J.; Singh, P.; Job, R.
- Journal of Organometallic Chemistry, Vol. 199, Issue 2
Electrochemistry in liquid sulfur dioxide. 4. Electrochemical production of highly oxidized forms of ferrocene, decamethylferrocene and iron bis(tris(1-pyrazolyl)borate)
journal, September 1983
- Sharp, Paul R.; Bard, Allen J.
- Inorganic Chemistry, Vol. 22, Issue 19
Reactivity of Electrochemically Generated Rhenium (II) Tricarbonyl α-Diimine Complexes: A Reinvestigation of the Oxidation of Luminescent Re(CO) 3 (α-Diimine)Cl and Related Compounds
journal, September 2008
- Bullock, John P.; Carter, Eric; Johnson, Ryan
- Inorganic Chemistry, Vol. 47, Issue 17
Photochemical reactions of fac-rhenium(I) tricarbonyl complexes and their application for synthesis
journal, January 2015
- Sato, Shunsuke; Ishitani, Osamu
- Coordination Chemistry Reviews, Vol. 282-283
Panchromatic Sensitization of Nanocrystalline TiO 2 with cis -Bis(4-carboxy-2-[2‘-(4‘-carboxypyridyl)]quinoline)bis(thiocyanato- N )ruthenium(II)
journal, December 2003
- Yanagida, Masatoshi; Yamaguchi, Takeshi; Kurashige, Mitsuhiko
- Inorganic Chemistry, Vol. 42, Issue 24
Molecular and electronic ground and excited structures of heteroleptic ruthenium polypyridyl dyes for nanocrystalline TiO2 solar cells
journal, January 2006
- Onozawa-Komatsuzaki, Nobuko; Kitao, Osamu; Yanagida, Masatoshi
- New Journal of Chemistry, Vol. 30, Issue 5
Cuprous Phenanthroline MLCT Chromophore Featuring Synthetically Tailored Photophysics
journal, September 2016
- Garakyaraghi, Sofia; Crapps, Peter D.; McCusker, Catherine E.
- Inorganic Chemistry, Vol. 55, Issue 20
Interfacial electron transfer yields in dye-sensitized NiO photocathodes correlated to excited-state dipole orientation of ruthenium chromophores
journal, September 2018
- Han, Yejee; Dillon, Robert J.; Flynn, Cory J.
- Canadian Journal of Chemistry, Vol. 96, Issue 9
Estimation of excited-state redox potentials by electron-transfer quenching. Application of electron-transfer theory to excited-state redox processes
journal, August 1979
- Bock, C. R.; Connor, J. A.; Gutierrez, A. R.
- Journal of the American Chemical Society, Vol. 101, Issue 17
Phosphonate-Based Bipyridine Dyes for Stable Photovoltaic Devices
journal, November 2001
- Gillaizeau-Gauthier, Isabelle; Odobel, Fabrice; Alebbi, Monica
- Inorganic Chemistry, Vol. 40, Issue 23
A Practical Beginner’s Guide to Cyclic Voltammetry
journal, November 2017
- Elgrishi, Noémie; Rountree, Kelley J.; McCarthy, Brian D.
- Journal of Chemical Education, Vol. 95, Issue 2
Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium–Tyrosine Complex
journal, November 2017
- Lennox, J. Christian; Dempsey, Jillian L.
- The Journal of Physical Chemistry B, Vol. 121, Issue 46
OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009
- Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
- Journal of Applied Crystallography, Vol. 42, Issue 2
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
The role of databases in support of computational chemistry calculations
journal, October 1996
- Feller, David
- Journal of Computational Chemistry, Vol. 17, Issue 13
Basis Set Exchange: A Community Database for Computational Sciences
journal, March 2007
- Schuchardt, Karen L.; Didier, Brett T.; Elsethagen, Todd
- Journal of Chemical Information and Modeling, Vol. 47, Issue 3
Works referencing / citing this record:
Realization of red shift of absorption spectra using optical near-field effect
journal, June 2019
- Yatsui, Takashi; Nakahira, Yusuke; Nakamura, Yuki
- Nanotechnology, Vol. 30, Issue 34
Inter-ligand intramolecular through-space anisotropic shielding in a series of manganese carbonyl phosphorous compounds
journal, January 2019
- Kurtz, Daniel A.; Dhakal, Badrinath; McDonald, Lauren T.
- Dalton Transactions, Vol. 48, Issue 39
A Rare Type of Rhenium(I) Diimine Complexes with Unsupported Coordinated Phosphine Oxide Ligands: Synthesis, Structural Characterization, Photophysical and Theoretical Study: A Rare Type of Rhenium(I) Diimine Complexes with Unsupported Coordinated Phosphine Oxide Ligands: Synthesis, Structural Characterization, Photophysica
journal, September 2019
- Nayeri, Sara; Jamali, Sirous; Pavlovskiy, Vladimir V.
- European Journal of Inorganic Chemistry, Vol. 2019, Issue 39-40
Addition of Re-Bonded Nucleophilic Ligands to Activated Alkynes: A Theoretical Rationalization: Addition of Re-Bonded Nucleophilic Ligands to Activated Alkynes: A Theoretical Rationalization
journal, January 2020
- Álvarez, Daniel; Díaz, Jesús; Menéndez, M. Isabel
- European Journal of Inorganic Chemistry, Vol. 2020, Issue 3
Experimental and computational exploration of photophysical and electroluminescent properties of modified 2,2′:6′,2″-terpyridine, 2,6-di(thiazol-2-yl)pyridine and 2,6-di(pyrazin-2-yl)pyridine ligands and their Re(I) complexes: Photopysics of Re(I) complexes - effect of donor-acceptor ligand
journal, October 2018
- Klemens, Tomasz; Świtlicka, Anna; Szlapa-Kula, Agata
- Applied Organometallic Chemistry, Vol. 32, Issue 12