Mesoscopic Donor−Acceptor Multilayer by Ultrahigh-Vacuum Codeposition of Zn-Tetraphenyl-Porphyrin and C70

The peculiar electrochemical and photophysical properties of porphyrin and fullerene molecules make them promising candidates for the construction of two- and three-dimensional organic-based materials. An important question is how pristine fullerene and porphyrin will organize when deposited on surfaces via in vacuum molecular beam evaporation. Here we show that codeposition of C70 and Zn-tetraphenyl-porphyrin (ZnTPP) induces the self-assembly of electron-rich flat aromatic molecules at the curved surface of C70, thus enhancing the chromophore interaction and forming a supramolecular multilayer donor−acceptor structure. While the ground-state electronic spectra almost reflect a simple summation of ZnTPP and C70 components, the excited-state electrons at the porphyrin macrocycle can rapidly delocalize to the fullerene. The excited charge transfer time scale is faster than 1−2 fs, as shown by resonant photoemission for the core-excited charges.