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Bespoke Photoreductants: Tungsten Arylisocyanides

Sattler, Wesley and Henling, Lawrence M. and Winkler, Jay R. and Gray, Harry B. (2015) Bespoke Photoreductants: Tungsten Arylisocyanides. Journal of the American Chemical Society, 137 (3). pp. 1198-1205. ISSN 0002-7863. doi:10.1021/ja510973h.

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Modular syntheses of oligoarylisocyanide ligands that are derivatives of 2,6-diisopropylphenyl isocyanide (CNdipp) have been developed; tungsten complexes incorporating these oligoarylisocyanide ligands exhibit intense metal-to-ligand charge-transfer visible absorptions that are red-shifted and more intense than those of the parent W(CNdipp)_6 complex. Additionally, these W(CNAr)_6 complexes have enhanced excited-state properties, including longer lifetimes and very high quantum yields. The decay kinetics of electronically excited W(CNAr)_6 complexes (*W(CNAr)_6) show solvent dependences; faster decay is observed in higher dielectric solvents. *W(CNAr)_6 lifetimes are temperature dependent, suggestive of a strong coupling nonradiative decay mechanism that promotes repopulation of the ground state. Notably, *W(CNAr)_6 complexes are exceptionally strong reductants: [W(CNAr)_6]+/*W(CNAr)_6 potentials are more negative than −2.7 V vs [Cp_2Fe]^+/Cp_2Fe.

Item Type:Article
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URLURL TypeDescription Information
Sattler, Wesley0000-0001-5316-260X
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2015 American Chemical Society. Received October 24, 2014. Publication Date (Web): January 16, 2015. We thank Michael Takase and David VanderVelde for assistance with X-ray and NMR experiments. Discussions with Aaron Rachford, Paul LaBeaume, Jim Thackeray, and Jim Cameron in the early stages of this work were very helpful. The Bruker KAPPA APEX II X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094). Our work is supported by the National Science Foundation Center for Chemical Innovation in Solar Fuels (CHE-1305124) and a CCI postdoctoral fellowship to W.S.
Group:CCI Solar Fuels
Funding AgencyGrant Number
NSF Postdoctoral FellowshipUNSPECIFIED
Issue or Number:3
Record Number:CaltechAUTHORS:20150126-093535146
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Official Citation:Bespoke Photoreductants: Tungsten Arylisocyanides Wesley Sattler, Lawrence M. Henling, Jay R. Winkler, and Harry B. Gray Journal of the American Chemical Society 2015 137 (3), 1198-1205 DOI: 10.1021/ja510973h
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:54064
Deposited By: Tony Diaz
Deposited On:26 Jan 2015 19:35
Last Modified:10 Nov 2021 20:28

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