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. https://resolver.caltech.edu/CaltechAUTHORS:20150126-093535146
![[img]](https://authors.library.caltech.edu/style/images/fileicons/application_pdf.png) |
PDF
- Supplemental Material
See Usage Policy. 4MB |
![[img]](https://authors.library.caltech.edu/style/images/fileicons/other.png) |
Crystallographic Info File (CIF)
- Supplemental Material
See Usage Policy. 5MB |
|
Crystallographic Info File (CIF)
- Supplemental Material
See Usage Policy. 67kB |
|
Crystallographic Info File (CIF)
- Supplemental Material
See Usage Policy. 90kB |
|
Crystallographic Info File (CIF)
- Supplemental Material
See Usage Policy. 48kB |
Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20150126-093535146
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: |
| ||||||||||||
| ORCID: |
| ||||||||||||
| 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: |
| ||||||||||||
| Issue or Number: | 3 | ||||||||||||
| DOI: | 10.1021/ja510973h | ||||||||||||
| 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: | 10 Nov 2021 20:28 |
Repository Staff Only: item control page
