Staniszewski Aaron, Heuer William B, Meyer Gerald J
Departments of Chemistry and Materials Science and Engineering, Johns Hopkins University, 400 North Charles Street, Baltimore, Maryland 21218,, USA.
Inorg Chem. 2008 Aug 18;47(16):7062-4. doi: 10.1021/ic800171h. Epub 2008 Mar 26.
The compounds Ru(bpy) 2(BTL)(PF 6) 2 and Ru(deeb) 2(BTL)(PF 6) 2, where bpy is 2,2'-bipyridine, deeb is 4,4'-(C 2H 5CO 2) 2-bpy, and BTL is 9'-[4,5-bis(cyanoethylthio)]-1,3-dithiol-2-ylidene]-4',5'-diazafluorene, were found to have very high extinction coefficients in the visible region. In an acetonitrile solution, the extinction of Ru(deeb) 2(BTL)(PF 6) 2 was = 44 000 +/- 1000 M (-1) cm (-1) at lambda = 470 nm. Two quasi-reversible oxidation waves, E 1/2 = +0.88 and +1.16 V, and an irreversible reduction, E pr = -1.6 V, were observed versus ferrocene (Fc (+/0)). At -40 degrees C, 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 TiO 2 with a quantum yield Phi = 0.3 +/- 0.2 for 532.5 or 417 nm light excitation in a 0.1 M LiClO 4/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.
化合物Ru(bpy)₂(BTL)(PF₆)₂和Ru(deeb)₂(BTL)(PF₆)₂，其中bpy为2,2'-联吡啶，deeb为4,4'-(C₂H₅CO₂)₂-bpy，BTL为9'-[4,5-双(氰基乙硫基)]-1,3-二硫醇-2-亚基]-4',5'-二氮杂芴，被发现在可见光区域具有非常高的消光系数。在乙腈溶液中，Ru(deeb)₂(BTL)(PF₆)₂在λ = 470 nm处的消光值为44000±1000 M⁻¹cm⁻¹。相对于二茂铁(Fc⁺/⁰)，观察到两个准可逆氧化波，E₁/₂ = +0.88和+1.16 V，以及一个不可逆还原波，Epr = -1.6 V。在-40℃时，观察到一种具有金属-配体电荷转移激发态光谱特性的状态，τ = 25 ns。在0.1 M LiClO₄/乙腈电解质中，对于532.5或417 nm光激发，发现该化合物以量子产率Φ = 0.3±0.2将电子光注入TiO₂。在再生太阳能电池中，观察到持续的光电流，最大入射光子-电流效率为0.4。光电流作用光谱和吸收光谱吻合良好，与从单一激发态注入一致。
