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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), Washington, D.C. (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0001011
OSTI ID:
1470299
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 9 Vol. 57; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (47)

Dual Emission from Rhenium(I) Complexes Induced by an Interligand Aromatic Interaction journal February 2012
The role of databases in support of computational chemistry calculations journal October 1996
Selective H2 and CO production with rhenium(I) biscarbonyl complexes as photocatalyst journal June 2012
Electrochemical and mechanistic studies of Re(CO)3(dmbpy)CI] and their relation to the catalytic reduction of CO2 journal April 1986
Efficient photocatalytic CO2 reduction using [Re(bpy) (CO)3{P(OEt)3}]+ journal May 1996
Photophysics of metal-organic π-conjugated polymers journal April 1998
Metallocene electrochemistry journal January 1980
Photochemical reactions of fac-rhenium(I) tricarbonyl complexes and their application for synthesis journal January 2015
Rhenium complexes in homogeneous hydrogen evolution journal December 2015
Electronic structures and spectral properties of rhenium(I) tricarbonyl diimine complexes with phosphine ligands: DFT/TDDFT theoretical investigations journal April 2012
Correlations between photophysical and electrochemical properties for a series of new Mn carbonyl complexes containing substituted phenanthroline ligands journal March 2015
Non-photochemical synthesis of Re(diimine)(CO)2(L)Cl (L = phosphine or phosphite) compounds journal September 2015
Medium effect on the equilibrium geometries, vibrational frequencies and solvation energies of sulfanilamide journal November 2010
Cuprous Phenanthroline MLCT Chromophore Featuring Synthetically Tailored Photophysics journal September 2016
A Practical Beginner’s Guide to Cyclic Voltammetry journal November 2017
Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium–Tyrosine Complex journal November 2017
Basis Set Exchange:  A Community Database for Computational Sciences journal March 2007
Proton-Coupled Electron Flow in Protein Redox Machines journal December 2010
Photophysical Behavior of a New CO2 Reduction Catalyst, Re(CO)2(bpy){P(OEt)3}2+ journal October 1994
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
Phosphonate-Based Bipyridine Dyes for Stable Photovoltaic Devices journal November 2001
Panchromatic Sensitization of Nanocrystalline TiO 2 with cis -Bis(4-carboxy-2-[2‘-(4‘-carboxypyridyl)]quinoline)bis(thiocyanato- N )ruthenium(II) journal December 2003
Preparative Routes to Luminescent Mixed-Ligand Rhenium(I) Dicarbonyl Complexes journal March 2006
Photochemical Ligand Substitution Reactions of fac -[Re(bpy)(CO) 3 Cl] and Derivatives journal March 2007
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
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
Application of the energy gap law to nonradiative, excited-state decay journal March 1983
Estimation of excited-state redox potentials by electron-transfer quenching. Application of electron-transfer theory to excited-state redox processes journal August 1979
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
Charge-Transfer Dynamics at the α/β Subunit Interface of a Photochemical Ribonucleotide Reductase journal January 2016
An Evaluation of Harmonic Vibrational Frequency Scale Factors journal November 2007
Diffusion-Limited Interfacial Electron Transfer with Large Apparent Driving Forces journal September 1999
Sensitization of Nanocrystalline TiO 2 Initiated by Reductive Quenching of Molecular Excited States journal February 1999
Luminescent Rhenium(I) Phenanthroline Complexes with a Benzoxazol-2-ylidene Ligand: Synthesis, Characterization, and Photophysical Study journal October 2012
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
Are Re( i ) phenanthroline complexes suitable candidates for OLEDs? Answers from DFT and TD-DFT investigations journal January 2014
New dinuclear hydrido-carbonyl rhenium complexes designed as photosensitizers in dye-sensitized solar cells journal January 2016
Molecular and electronic ground and excited structures of heteroleptic ruthenium polypyridyl dyes for nanocrystalline TiO2 solar cells journal January 2006
Photosensitized generation of singlet oxygen from rhenium(i) and iridium(iii) complexes journal January 2007
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
Photophysical properties of polypyridyl carbonyl complexes of rhenium(I) journal January 1991
Photo-ribonucleotide reductase  2 by selective cysteine labeling with a radical phototrigger journal December 2011
The Luminescence Rigidochromic Effect Exhibited by Organometallic Complexes: Rationale and Applications journal November 1995
OLEX2 : a complete structure solution, refinement and analysis program journal January 2009
A short history of SHELX journal December 2007
Tryptophan-Accelerated Electron Flow Through Proteins journal June 2008
Interfacial electron transfer yields in dye-sensitized NiO photocathodes correlated to excited-state dipole orientation of ruthenium chromophores journal September 2018

Cited By (5)

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
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
Inter-ligand intramolecular through-space anisotropic shielding in a series of manganese carbonyl phosphorous compounds journal January 2019
Realization of red shift of absorption spectra using optical near-field effect journal June 2019

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