Remarkably Efficient Photocurrent Generation Based on a [60]Fullerene-Triosmium Cluster/Zn-Porphyrin/Boron-Dipyrrin Triad SAM

A new artificial photosynthetic triad array, a [60]fullerene–triosmium cluster/zinc–porphyrin/boron–dipyrrin complex (1, Os3C60/ZnP/Bodipy), has been prepared by decarbonylation of Os3(CO)8(CN(CH2)3Si(OEt)3)(μ3‐η2:η2:η2‐C60) (6) with Me3NO/MeCN and subsequent reaction with the isocyanide ligand CNZnP/Bodipy (5) containing zinc porphyrin (ZnP) and boron dipyrrin (Bodipy) moieties. Triad 1 has been characterized by various spectroscopic methods (MS, NMR, IR, UV/Vis, photoluminescence, and transient absorption spectroscopy). The electrochemical properties of 1 in chlorobenzene (CB) have been examined by cyclic voltammetry; the general feature of the cyclic voltammogram of 1 is nine reversible one‐electron redox couples, that is, the sum of those of 5 and 6. DFT has been applied to study the molecular and electronic structures of 1. On the basis of fluorescence‐lifetime measurements and transient absorption spectroscopic data, 1 undergoes an efficient energy transfer from Bodipy to ZnP and a fast electron transfer from ZnP to C60; the detailed kinetics involved in both events have been elucidated. The SAM of triad 1 (1/ITO; ITO=indium–tin oxide) has been prepared by immersion of an ITO electrode in a CB solution of 1 and diazabicyclo‐octane (2:1 equiv), and characterized by UV/Vis absorption spectroscopy, water contact angle, X‐ray photoelectron spectroscopy, and cyclic voltammetry. The photoelectrochemical properties of 1/ITO have been investigated by a standard three‐electrode system in the presence of an ascorbic acid sacrificial electron donor. The quantum yield of the photoelectrochemical cell has been estimated to be 29 % based on the number of photons absorbed by the chromophores. Our triad 1 is unique when compared to previously reported photoinduced electron‐transfer arrays, in that C60 is linked by π bonding with little perturbation of the C60 electron delocalization. Unique molecular characteristics of the cluster arrays of the title triad (see graphic, ITO=indium–tin oxide) give rise to a remarkably high quantum yield of the photoelectrochemical cell comprising a standard three‐electrode system with an ascorbic acid sacrificial electron donor. It is hoped that similar SAMs may prove useful in molecular electronic devices.