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Title: Synthesis, Electrochemistry, and Excited-State Properties of Three Ru(II) Quaterpyridine Complexes

Abstract

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 CH 3CN exhibit broad metal-to-ligand charge transfer (MLCT) absorptions arising from overlapping 1A 1 → 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 CH 3CN reveal the expected RuIII/II redox couples. In 0.1 M trifluoroacetic acid (TFA), 1 and 2 undergo aquation to give [RuII(qpy)(OH 2) 2] 2+, as evidenced by the appearance of waves for the couples [RuIII(qpy)(OH 2) 2] 3+/[RuII(qpy)(OH 2) 2] 2+, [RuIV(qpy)(O)(OH 2)] 2+/[RuIII(qpy)(OH 2) 2] 3+, and [RuVI(qpy)(O) 2] 2+/[RuIV(qpy)(O)(OH 2)] 2+ in cyclic voltammograms.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1]
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  1. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
Publication Date:
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)
OSTI Identifier:
1241400
Alternate Identifier(s):
OSTI ID: 1387513
Grant/Contract Number:  
SC0001011; AC05- 06OR23100
Resource 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
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

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., 2016. Web. doi:10.1021/acs.jpca.6b00317.
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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.
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Rudd, Jennifer A., Brennaman, M. Kyle, Michaux, Katherine E., Ashford, Dennis L., Murray, Royce W., and Meyer, Thomas. J. Wed . "Synthesis, Electrochemistry, and Excited-State Properties of Three Ru(II) Quaterpyridine Complexes". United States. doi:10.1021/acs.jpca.6b00317.
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@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}
}
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Publisher's Version of Record
DOI: 10.1021/acs.jpca.6b00317
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Works referencing / citing this record:

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  • Chemistry - A European Journal, Vol. 23, Issue 19
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Lattice interactions of terpyridines and their derivatives – free terpyridines and their protonated forms
journal, January 2016

  • Lee, Young Hoon; Kim, Jee Young; Kim, Yang
  • CrystEngComm, Vol. 18, Issue 41
  • DOI: 10.1039/c6ce01435f
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