Relaxation processes in self-assembling triads based on porphyrin Zn-heterodimers

The directional self-assembly of nanosized, structurally organized triads is implemented in methylcyclohexane at 295 K, which is based on the two-point extra coordination of nonsymmetric, covalently bound heterodimers of Zn porphyrins to bipyridyl-substituted porphyrin free-base extra ligands. Based on experimental data and theoretical calculations, the structural organization is determined and information on the energetics of electronic interactions of components is obtained and the rate constants of the directional energy transfer (k ET ∼ 1011 s−1) and photoinduced electron transfer (k PET ∼ 2.7 × 109 s−1) are determined. The effects of the orientation of interacting macrocycles, the intercenter distances and the solvent temperature on the efficiency of relaxation processes in the triad is investigated.