Bingöl, Bahar and Durrell, Alec C. and Keller, Gretchen E. and Palmer, Joshua H. and Grubbs, Robert H. and Gray, Harry B. (2013) Electron Transfer Triggered by Optical Excitation of Phenothiazin-tris(meta-phenylene-ethynylene)-(tricarbonyl)(bpy)(py)rhenium(I). Journal of Physical Chemistry B, 117 (16). pp. 4177-4182. ISSN 1520-6106. http://resolver.caltech.edu/CaltechAUTHORS:20130606-115526109
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Abstract
We have investigated excited-state electron transfer in a donor-bridge-acceptor complex containing phenothiazine (PTZ) linked via tris(meta-phenylene-ethynylene) to a tricarbonyl(bipyridine)(pyridine)Re(I) unit. Time-resolved luminescence experiments reveal two excited-state (*Re) decay regimes, a multiexponential component with a mean lifetime of 2.7 ns and a longer monoexponential component of 530 ns in dichloromethane solution. The faster decay is attributed to PTZ → *Re electron transfer in a C-shaped PTZ-bridge-Re conformer (PTZ–Re ≈ 7.5 Å). We assign the longer lifetime, which is virtually identical to that of free *Re, to an extended conformer (PTZ–Re > 20 Å). The observed biexponential *Re decay requires that interconversion of PTZ-bridge-Re conformers be slower than 10^6 s^(–1).
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| Alternate Title: | Electron Transfer Triggered by Optical Excitation of Phenothiazinetris(meta-phenylene-ethynylene)-(tricarbonyl)(bpy)(py)rhenium(I) | |||||||||
| Additional Information: | © 2012 American Chemical Society. Received: January 31, 2012; Revised: April 9, 2012; Published: April 25, 2012. Dedicated to the memory of Paul Barbara, a great scientist and dear friend. We thank Tony Vlcek for many helpful discussions and Angelo Di Bilio for assistance with EPR experiments. Supported by a NSF Center for Chemical Innovation grant (Powering the Planet CHE-0802907) and the Arnold and Mabel Beckman Foundation. | |||||||||
| Group: | CCI Solar Fuels | |||||||||
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| Record Number: | CaltechAUTHORS:20130606-115526109 | |||||||||
| Persistent URL: | http://resolver.caltech.edu/CaltechAUTHORS:20130606-115526109 | |||||||||
| Official Citation: | Electron Transfer Triggered by Optical Excitation of Phenothiazine-tris(meta-phenylene-ethynylene)-(tricarbonyl)(bpy)(py)rhenium(I) Bahar Bingöl, Alec C. Durrell, Gretchen E. Keller, Joshua H. Palmer, Robert H. Grubbs, and Harry B. Gray The Journal of Physical Chemistry B 2013 117 (16), 4177-4182 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 38837 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Jason Perez | |||||||||
| Deposited On: | 06 Jun 2013 22:36 | |||||||||
| Last Modified: | 07 Dec 2016 23:43 |
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