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Title: Bathochromic Shifts in Rhenium Carbonyl Dyes Induced through Destabilization of Occupied Orbitals

Journal Article · · Inorganic Chemistry
 [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
+ Show Author Affiliations

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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001011
OSTI ID:
1470299
Journal Information:
Inorganic Chemistry, Vol. 57, 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; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 41 works
Citation information provided by
Web of Science

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Cited By (4)

Realization of red shift of absorption spectra using optical near-field effect journal June 2019
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
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
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

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