Abstract
Two triads (i.e., 3PTZ–Pt–MNDI and 10PTZ–Pt–MNDI) consisting of 3-phenothiazine (3PTZ) or 10-phenothiazine (10PTZ), bipyridine–diacetylide platinum complex (Pt), and naphthalene diimide (MNDI) chromophores linked by highly twisted biphenylene spacers have been prepared. The formation and decay of the charge-separated (CS) states in toluene were studied by use of picosecond and nanosecond laser photolysis via selective excitation of the Pt moiety. The time required for formation of the CS state, PTZ+–Pt–MNDI−, from PTZ–3Pt*–MNDI was determined to be τ CS = 280 ps for 3PTZ+–Pt–MNDI− and τ CS = 230 ps for 10PTZ+–Pt–MNDI−. The lifetimes of the CS states were determined to be τ CR1 = 75 ns (95 %) and τ CR2 = 285 ns (5 %) for 3PTZ+–Pt–MNDI− and τ CR = 830 ns for 10PTZ+–Pt–MNDI−. Formation and decay of the CS states are discussed in terms the Marcus theory and the spin-correlated radical pair mechanism.
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Notes
The quantum yields for the formation of CS states for the excitation of 2 and 3 were estimated by using the relative intensities of 3Pt* (650 nm) and MNDI− (470 nm) in the ps-laser photolysis (Fig. 5).
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Acknowledgments
This work was supported by Grants-in-Aid: for Scientific Research (B) (no. 2350066 for K.O.), for Young Scientists (B) (no. 22750043 for S.S.), and for JSPS Fellows (no. 238419 for R.S.) from the Japan Society for Promotion of Science (JSPS). S.S. is also grateful for financial support from the Kansai Research Foundation for Technology Promotion and the Association for the Progress of New Chemistry.
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Sugimura, R., Suzuki, S., Kozaki, M. et al. Photoinduced charge separation of phenothiazine–platinum–naphthalene diimide triads linked by twisted phenylene bridges. Res Chem Intermed 39, 185–204 (2013). https://doi.org/10.1007/s11164-012-0642-6
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DOI: https://doi.org/10.1007/s11164-012-0642-6