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Published January 28, 2015 | Version Supplemental Material
Journal Article Open

Bespoke Photoreductants: Tungsten Arylisocyanides

Creators

  • 1. ROR icon California Institute of Technology

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.

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.

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Supplemental Material - ja510973h_si_005.pdf

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Additional details

Identifiers

Eprint ID
54064
DOI
10.1021/ja510973h
Resolver ID
CaltechAUTHORS:20150126-093535146

Related works

Describes
10.1021/ja510973h (DOI)

Funding

NSF
CHE-0639094
NSF
CHE-1305124
NSF Postdoctoral Fellowship

Dates

Created
2015-01-26
Created from EPrint's datestamp field
Updated
2021-11-10
Created from EPrint's last_modified field

Caltech Custom Metadata

Caltech groups
CCI Solar Fuels