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High-Extinction Ruthenium Compounds for Sunlight Harvesting and Hole Transport

机译：用于阳光收获和空穴传输的高消光钌化合物

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The compounds Ru(bpy)2(BTL)(PF6)2 and Ru(deeb)2(BTL)(PF6)2, where bpy is2,2(prime)-bipyridine, deeb is 4,4(prime)-(C2H5CO2)2-bpy, and BTL is 9(prime)- 4,5-bis(cyanoethylthio) -(1,3-dithiol-2-ylidene) -4(prime),5(prime)- diazafluorene, were found to have very high extinction coefficients in the visible region. In an acetonitrile solution, the extinction of Ru(deeb)2(BTL)(PF6)2 was epsilon = 44 000 plus/minus 1000 M(exp -1) cm(exp )-1 at lambda = 470 nm. Two quasi-reversible oxidation waves, E(sub 1/2) = +0.88 and +1.16 V, and anirreversible reduction, E(sub pr) = -1.6 V, were observed versus ferrocene (Fc(exp +/0)). At -40 degrees Celsius, a state was observed with spectroscopic properties characteristic of a metal-to-ligand charge- transfer excited state, tau = 25 ns. This same compound was found to photoinject electrons into TiO2 with a quantum yield phi = 0.3 plus/minus 0.2 for 532.5 or 417 nm light excitation in a 0.1 M LiClO4/acetonitrile electrolyte. In regenerative solar cells, a sustained photocurrent was observed with a maximum incident photon-to-current efficiency of 0.4. The photocurrent action and absorptance spectra were in good agreement, consistent with injection from a single excited state.

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