Synthesis, Electrochemistry, and Excited-State Properties of Three Ru(II) Quaterpyridine Complexes
The complexes [Ru(qpy)LL']2+ (qpy = 2,2':6',2'':6'',2''-quaterpyridine), with 1: L = acetonitrile, L'= chloride; 2: L = L'= acetonitrile; and 3: L = L'= vinylpyridine, have been prepared from [Ru(qpy) (Cl)2]. Their absorption spectra in CH3CN exhibit broad metal-to-ligand charge transfer (MLCT) absorptions arising from overlapping 1A1 → 1MLCT transitions. Photoluminescence is not observed at room temperature, but all three are weakly emissive in 4:1 ethanol/methanol glasses at 77 K with broad, featureless emissions observed between 600 and 1000 nm consistent with MLCT phosphorescence. Cyclic voltammograms in CH3CN reveal the expected RuIII/II redox couples. In 0.1 M trifluoroacetic acid (TFA), 1 and 2 undergo aquation to give [RuII(qpy)(OH2)2]2+, as evidenced by the appearance of waves for the couples [RuIII(qpy)(OH2)2]3+/[RuII(qpy)(OH2)2]2+, [RuIV(qpy)(O)(OH2)]2+/[RuIII(qpy)(OH2)2]3+, and [RuVI(qpy)(O)2]2+/[RuIV(qpy)(O)(OH2)]2+ in cyclic voltammograms.
- Authors:
-
[1]
; [1]
; [1]
; [1]
; [1]
; [1]
- Department of Chemistry, University of North Carolina at Chapel Hill, CB 3290, Chapel Hill, North Carolina 27599-3290, United States
- Publication Date:
- Grant/Contract Number:
- SC0001011; AC05- 06OR23100
- Type:
- Published Article
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 120; Journal Issue: 11; 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 1089-5639
- Publisher:
- American Chemical Society
- 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) (SC-22)
- 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)
- OSTI Identifier:
- 1241400
- Alternate Identifier(s):
- OSTI ID: 1387513
Rudd, Jennifer A., Brennaman, M. Kyle, Michaux, Katherine E., Ashford, Dennis L., Murray, Royce W., and Meyer, Thomas. J.. Synthesis, Electrochemistry, and Excited-State Properties of Three Ru(II) Quaterpyridine Complexes. United States: N. p.,
Web. doi:10.1021/acs.jpca.6b00317.
Rudd, Jennifer A., Brennaman, M. Kyle, Michaux, Katherine E., Ashford, Dennis L., Murray, Royce W., & Meyer, Thomas. J.. Synthesis, Electrochemistry, and Excited-State Properties of Three Ru(II) Quaterpyridine Complexes. United States. doi:10.1021/acs.jpca.6b00317.
Rudd, Jennifer A., Brennaman, M. Kyle, Michaux, Katherine E., Ashford, Dennis L., Murray, Royce W., and Meyer, Thomas. J.. 2016.
"Synthesis, Electrochemistry, and Excited-State Properties of Three Ru(II) Quaterpyridine Complexes". United States.
doi:10.1021/acs.jpca.6b00317.
@article{osti_1241400,
title = {Synthesis, Electrochemistry, and Excited-State Properties of Three Ru(II) Quaterpyridine Complexes},
author = {Rudd, Jennifer A. and Brennaman, M. Kyle and Michaux, Katherine E. and Ashford, Dennis L. and Murray, Royce W. and Meyer, Thomas. J.},
abstractNote = {The complexes [Ru(qpy)LL']2+ (qpy = 2,2':6',2'':6'',2''-quaterpyridine), with 1: L = acetonitrile, L'= chloride; 2: L = L'= acetonitrile; and 3: L = L'= vinylpyridine, have been prepared from [Ru(qpy) (Cl)2]. Their absorption spectra in CH3CN exhibit broad metal-to-ligand charge transfer (MLCT) absorptions arising from overlapping 1A1 → 1MLCT transitions. Photoluminescence is not observed at room temperature, but all three are weakly emissive in 4:1 ethanol/methanol glasses at 77 K with broad, featureless emissions observed between 600 and 1000 nm consistent with MLCT phosphorescence. Cyclic voltammograms in CH3CN reveal the expected RuIII/II redox couples. In 0.1 M trifluoroacetic acid (TFA), 1 and 2 undergo aquation to give [RuII(qpy)(OH2)2]2+, as evidenced by the appearance of waves for the couples [RuIII(qpy)(OH2)2]3+/[RuII(qpy)(OH2)2]2+, [RuIV(qpy)(O)(OH2)]2+/[RuIII(qpy)(OH2)2]3+, and [RuVI(qpy)(O)2]2+/[RuIV(qpy)(O)(OH2)]2+ in cyclic voltammograms.},
doi = {10.1021/acs.jpca.6b00317},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 11,
volume = 120,
place = {United States},
year = {2016},
month = {3}
}