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

다국어 초록 (Multilingual Abstract)

<P>A new artificial photosynthetic triad array, a [60]fullerene–triosmium cluster/zinc–porphyrin/boron–dipyrrin complex (1, Os<SUB>3</SUB>C<SUB>60</SUB>/ZnP/Bodipy), has been prepared by decarbonylation of Os<SUB>3</SUB>(CO)<SUB>8</SUB>(CN(CH<SUB>2</SUB>)<SUB>3</SUB>Si(OEt)<SUB>3</SUB>)(μ<SUB>3</SUB>-η<SUP>2</SUP>:η<SUP>2</SUP>:η<SUP>2</SUP>-C<SUB>60</SUB>) (6) with Me<SUB>3</SUB>NO/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 C<SUB>60</SUB>; 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 C<SUB>60</SUB> is linked by π bonding with little perturbation of the C<SUB>60</SUB> electron delocalization.</P>
<B>Graphic Abstract</B>
<P>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.
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