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Published May 1, 1994 | Supplemental Material
Journal Article Open

Photoinduced Electron Transfer in Iridium(spacer)pyridinium Complexes

Abstract

Photoinduced electron-transfer (ET) reactions in a series of iridium(spacer)pyridinium complexes, [Ir(µ-pz*)-(CO)Ph_2POC_6H_4(CH_2)_n-A^+]_2 (pz* = 3,5-dimethylpyrazolyI; Ph = C_6H_5; C_6H_4 = phenylene; A^+ = pyridinium (py^+) or substituted py^+; n = 0-3), have been studied in acetonitrile solution at room temperature. The rates of singlet (^1Irz* → A^+: ^1ET) reactions were determined for each complex, and for n = 1 and 2 species, the rates of thermal charge recombination (ET^b) also were measured. The ET rates for the n = 1 system display a Gaussian free-energy dependence ( λ = 1.0 eV, H_(AB) = 5 cm^(-1)). With one exception, maximum ET rates exhibit an exponential dependence upon the number of carbon atoms (α_c) in the spacer. The exception is the n = 1 (α_c = 5) system; k_(max) is almost a factor of 100 slower than predicted by the exponential dependence on α_c, indicating that donor-acceptor electronic coupling through a single methylene link is unusually weak.

Additional Information

© 1994 American Chemical Society. Received: December 17, 1993; In Final Form: March 30, 1994. Research at the California Institute of Technology was supported by NSF Grants CHE-8922067 and CHE-9311587. Research carried out at Brookhaven National Laboratory was under contract DE-AC02-76CH00016 with the US. Department of Energy and supported by its Division of Chemical Sciences, Office of Basic Research. R.S.F. thanks the US. Department of Education for a graduate fellowship.

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