Remarkably efficient photocurrent generation based on a [60] fullerence-triosmium cluster/Zn-porphyrin/boron-dipyrrin triad SAM

Chang Yeon Lee, Jae Kwon Jang, Chul Hoon Kim, Jaehoon Jung, Bo Keun Park, Jihee Park, Wonyong Choi, Young Kyu Han, Taiha Joo, Joon T. Park

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56 Scopus citations

Abstract

A new artificial photosynthetic triad array, a [60]fullerene-triosmium cluster/zinc-porphyrin/boron-dipyrrin complex (1, Os3C 60/ZnP/ Bodipy), has been prepared by decarbonylation of Os 3(CO)8(CN(CH2)3Si(OEt) 3)(μ322: 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 diaza bicyclo-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 derealization.

Original languageEnglish
Pages (from-to)5586-5599
Number of pages14
JournalChemistry - A European Journal
Volume16
Issue number19
DOIs
StatePublished - 17 May 2010

Keywords

  • Electron transfer
  • Monolayers
  • Photoelectrochemistry
  • Self-assembly
  • Triads

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