Energy migration in a self-assembled nonameric porphyrinic molecular box

We describe the construction of self-assembled double-decker porphyrin arrays built up from two covalently connected trimeric Zn-porphyrin units that are joined together by metal-coordination bonds with diamine ligands. We used three different types of diamine ligands: 1,4-diaza[2.2.2]bicyclooctane (DABCO), 4,4'-bipyridine (BIPY), and 5,15-bis(4-pyridyl)-10,20-diphenylporphyrin (DPYP). The ligands act as pillars, through two axial coordination bonds with the porphyrinic Zn(II) ions, to block the planes of the porphyrin units in an almost cofacial orientation and inducing the formation of a trigonal prismatic structure. The spectroscopic and photophysical properties of the Zn-trisporphyrin component were determined as well as those of the resulting multimolecular cagelike assemblies. The double-decker assembly with DPYP as the pillars constitutes a nonameric porphyrin aggregate. Although this assembly is thermodynamically less stable than those containing DABCO or BIPY, efficient photoinduced energy transfer occurs (96% yield) from the trisporphyrin base units to the DPYP side walls. The rate of the energy-transfer process is in good agreement with that calculated for a dipole-dipole (F?rster) mechanism corrected for the unfavorable orientation geometry of the donor and the axially bound acceptor.