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Title: 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(NCCH 3)] + (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:
 [1]; ORCiD logo [1];  [1];  [2];  [3]; ORCiD logo [1]; ORCiD logo [4]
  1. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
  2. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; National Univ. of Singapore (Singapore). Dept. of Chemistry
  3. Eckerd College, St. Petersburg, FL (United States). Dept. of Chemistry
  4. 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), Washington, D.C. (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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. 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., and Dempsey, Jillian L. Thu . "Bathochromic Shifts in Rhenium Carbonyl Dyes Induced through Destabilization of Occupied Orbitals". United States. doi: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 = {2018},
month = {4}
}

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