skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Photoinduced electron transfer from rylenediimide radical anions and dianions to Re(bpy)(CO)3 using red and near-infrared light

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c6sc05103k· OSTI ID:1425912

A major goal of artificial photosynthesis research is photosensitizing highly reducing metal centers using as much as possible of the solar spectrum reaching Earth's surface. The radical anions and dianions of rylenediimide (RDI) dyes, which absorb at wavelengths as long as 950 nm, are powerful photoreductants with excited state oxidation potentials that rival or exceed those of organometallic chromophores. These dyes have been previously incorporated into all-organic donor–acceptor systems, but have not yet been shown to reduce organometallic centers. This study describes a set of dyads in which perylenediimide (PDI) or naphthalenediimide (NDI) chromophores are attached to Re(bpy)(CO)3 through either the bipyridine ligand or more directly to the Re center via a pyridine ligand. The chromophores are reduced with a mild reducing agent, after which excitation with long-wavelength red or near-infrared light leads to reduction of the Re complex. The kinetics of electron transfer from the photoexcited anions to the Re complex are monitored using transient visible/near-IR and mid-IR spectroscopy, complemented by theoretical spectroscopic assignments. The photo-driven charge shift from the reduced PDI or NDI to the complex occurs in picoseconds regardless of whether PDI or NDI is attached to the bipyridine or to the Re center, but back electron transfer is found to be three orders of magnitude slower with the chromophore attached to the Re center. These results will inform the design of future catalytic systems that incorporate RDI anions as chromophores.

Research Organization:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001059
OSTI ID:
1425912
Journal Information:
Chemical Science, Vol. 8, Issue 5; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 53 works
Citation information provided by
Web of Science

References (36)

Photodriven Electron and Energy Transfer from Copper Phenanthroline Excited States journal January 1996
Femtosecond Optical Switching of Electron Transport Direction in Branched Donor−Acceptor Arrays journal February 2000
Excited Doublet States of Electrochemically Generated Aromatic Imide and Diimide Radical Anions journal July 2000
Bespoke Photoreductants: Tungsten Arylisocyanides journal January 2015
Photo-driven electron transfer from the highly reducing excited state of naphthalene diimide radical anion to a CO 2 reduction catalyst within a molecular triad journal January 2017
Tuning the Excited-State Properties of Platinum(II) Diimine Dithiolate Complexes journal January 1996
Why Is Re−Re Bond Formation/Cleavage in [Re(bpy)(CO) 3 ] 2 Different from That in [Re(CO) 5 ] 2 ? Experimental and Theoretical Studies on the Dimers and Fragments journal November 2004
Electron Transfer from the Porphyrin S 2 State in a Zinc Porphyrin-Rhenium Bipyridyl Dyad having Carbon Dioxide Reduction Activity journal May 2009
Reaction of the 2-(bromodifluoromethyl)benzoxazole with tetrakis(dimethylamino)ethylene (TDAE) in the presence of aldehydes. A convenient synthesis of 2-(difluoromethyl)benzoxazole alcohols journal February 1997
Photoinduced Intramolecular Tryptophan Oxidation and Excited-State Behavior of [Re(L-AA)(CO) 3 (α-diimine)] + (L = Pyridine or Imidazole, AA = Tryptophan, Tyrosine, Phenylalanine) journal July 2011
Generation of Powerful Tungsten Reductants by Visible Light Excitation journal July 2013
Development of highly efficient supramolecular CO 2 reduction photocatalysts with high turnover frequency and durability journal January 2012
Involvement of a Binuclear Species with the Re−C(O)O−Re Moiety in CO 2 Reduction Catalyzed by Tricarbonyl Rhenium(I) Complexes with Diimine Ligands:  Strikingly Slow Formation of the Re−Re and Re−C(O)O−Re Species from Re(dmb)(CO) 3 S (dmb = 4,4‘-Dimethyl-2,2‘-bipyridine, S = Solvent) journal October 2003
Improving the Efficiency of the Photoinduced Charge-Separation Process in a Rhenium(I)–Zinc Porphyrin Dyad by Simple Chemical Functionalization journal March 2013
Ultrafast Excited-State Dynamics of Rhenium(I) Photosensitizers [Re(Cl)(CO) 3 (N,N)] and [Re(imidazole)(CO) 3 (N,N)] + : Diimine Effects journal April 2011
Ultrafast Molecular Logic Gate Based on Optical Switching between Two Long-Lived Radical Ion Pair States journal March 2001
Re(bipy-tBu)(CO) 3 Cl−improved Catalytic Activity for Reduction of Carbon Dioxide: IR-Spectroelectrochemical and Mechanistic Studies journal October 2010
Developing a Mechanistic Understanding of Molecular Electrocatalysts for CO 2 Reduction using Infrared Spectroelectrochemistry journal April 2014
Intermolecular and Intramolecular Electron Transfer Processes from Excited Naphthalene Diimide Radical Anions journal November 2014
CO2 photoreduction with long-wavelength light: dyads and monomers of zinc porphyrin and rhenium bipyridine journal January 2012
A Highly Emissive Cu 2 N 2 Diamond Core Complex Supported by a [PNP] - Ligand journal February 2005
Ultrafast Charge Separation in a Photoreactive Rhenium-Appended Porphyrin Assembly Monitored by Picosecond Transient Infrared Spectroscopy journal April 2006
Excited-state properties of a triply ortho-metalated iridium(III) complex journal March 1985
Unprecedented Intramolecular Electron Transfer from Excited Perylenediimide Radical Anion journal June 2016
Electrocatalytic Reduction of CO2 Using the Complexes [Re(bpy)(CO)3L]n (n = +1, L = P(OEt)3, CH3CN; n = 0, L = Cl-, Otf-; bpy = 2,2‘-Bipyridine; Otf- = CF3SO3) as Catalyst Precursors:  Infrared Spectroelectrochemical Investigation journal July 1996
Electrochemical Properties and CO 2 -Reduction Ability of m -Terphenyl Isocyanide Supported Manganese Tricarbonyl Complexes journal November 2016
Ultrafast Conformational Dynamics of Electron Transfer in ExBox 4+ ⊂Perylene journal November 2013
Photochemistry and Photophysics of Coordination Compounds: Iridium book January 2007
Photochemistry and Photophysics of a Pd(II) Metalloporphyrin: Re(I) Tricarbonyl Bipyridine Molecular Dyad and its Activity Toward the Photoreduction of CO 2 to CO journal December 2011
Picosecond Control of Photogenerated Radical Pair Lifetimes Using a Stable Third Radical journal April 2016
Red-Light-Driven Photocatalytic Reduction of CO 2 using Os(II)–Re(I) Supramolecular Complexes journal September 2013
A light-induced redox reaction of bis(2,9-dimethyl-1,10-phenanthroline)copper(I) journal April 1977
Iridium(III) 1-Phenylisoquinoline Complexes as a Photosensitizer for Photocatalytic CO 2 Reduction: A Mixed System with a Re(I) Catalyst and a Supramolecular Photocatalyst journal May 2016
Stable Aromatic Dianion in Water journal July 2008
Chemical Redox Agents for Organometallic Chemistry journal January 1996
Optical parametric amplification of femtosecond pulses tunable from the blue to the infrared with microjoule energies journal January 1995

Cited By (5)

Stable Bifunctional Perylene Imide Radicals for High-Performance Organic-Lithium Redox-Flow Batteries journal August 2018
Naphthalenediimide (NDI)-Conjugated Foldable Polyurethanes: Impact of Chromophoric Location on Hierarchical Supramolecular Assembly and Conductivity journal June 2018
α-Benzyl-β-Alanine Containing Naphthalenediimide Promotes Photoresponsive Radical Anion journal September 2018
Electron-poor arylenediimides journal January 2018
Doubly zwitterionic, di-reduced, highly electron-rich, air-stable naphthalenediimides: redox-switchable islands of aromatic–antiaromatic states journal January 2019