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Electron Transfer Triggered by Optical Excitation of Phenothiazin-tris(meta-phenylene-ethynylene)-(tricarbonyl)(bpy)(py)rhenium(I)

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. doi:10.1021/jp3010053.

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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).

Item Type:Article
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Grubbs, Robert H.0000-0002-0057-7817
Gray, Harry B.0000-0002-7937-7876
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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Arnold and Mabel Beckman FoundationUNSPECIFIED
Issue or Number:16
Record Number:CaltechAUTHORS:20130606-115526109
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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
Deposited On:06 Jun 2013 22:36
Last Modified:09 Nov 2021 23:40

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