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Excited-State Equilibration over 30 Å in a Platinum(II) Quinolinolate−Bridge−Platinum(II) Porphyrin Complex

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Victor A. Montes, Michael A. J. Rodgers, and Pavel Anzenbacher, Jr.*

Department of Chemistry and Center for Photochemical Sciences, Bowling Green State University, Bowling Green, Ohio 43403

Inorg. Chem., 2007, 46 (25), pp 10464–10466

DOI: 10.1021/ic701557q

Publication Date (Web): November 8, 2007

To whom correspondence should be addressed. E-mail: pavel@ bgsu.edu.

Abstract

Long-range triplet excited-state equilibration occurs over a nanometric distance between platinum(II) 8-quinolinolate (³Ptq₂ = 1.87 eV) and platinum(II) tetraphenylporphyrin (³PtTPP = 1.89 eV). The equilibrium is mediated by a fluorene−thiophene−fluorene bridge (³FTF = 1.92 eV) and is characterized by a double-exponential decay (τ₁ = 39 ± 4 ps; τ₂ = 351 ± 15 ps) that suggests the participation of three separate excited states: ³Ptq₂, ³FTF, and ³PtTPP, respectively. Numerical simulation of the dual equilibrium allowed for estimation of the individual rate constants for each of the reversible steps (k_ET = 3.9 × 10⁹−4.1 × 10¹⁰ s^-1). As a result of rapid triplet-state equilibration, almost 50% of the excited-state energy is directed from the PtTPP chromophore toward Ptq₂, in spite of a small endothermic barrier (0.03 eV).

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Published In Issue December 10, 2007
Received August 3, 2007

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Communication

Excited-State Equilibration over 30 Å in a Platinum(II) Quinolinolate−Bridge−Platinum(II) Porphyrin Complex