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Published April 25, 2013 | Supplemental Material
Journal Article Open

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


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).

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.

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