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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. https://resolver.caltech.edu/CaltechAUTHORS:20150126-093535146

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Abstract

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
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja510973hDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja510973hPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja510973hPublisherSupporting Information
ORCID:
AuthorORCID
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
Funders:
Funding AgencyGrant Number
NSFCHE-0639094
NSFCHE-1305124
NSF Postdoctoral FellowshipUNSPECIFIED
Issue or Number:3
Record Number:CaltechAUTHORS:20150126-093535146
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150126-093535146
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
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:26 Jan 2015 19:35
Last Modified:22 Nov 2019 09:58

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