Low-lying activated states of chloroiridium phthalocyanine aggregates in glassy solution at low temperatures

Studies of phosphorescence intensities and lifetimes of two chloroiridium phthalocyanine aggregates in α-chloronaphthalene between 5 and 80 K have revealed the existence of low-lying activated states only a few tens of cm−1 above the zero-point vibration in both lowest singlet and triplet states. From the data, activation energies of intersystem crossings between the two multiplicities associated with these states have been obtained as follows: for crossing from the first excited singlet to the lowest triplet state, Ea = 42 ± 10 and 29 ± 10 cm−1, respectively, for the two aggregates; for crossing from the lowest triplet to the ground singlet state, [Formula: see text] and 23 ± 5 cm−1, respectively. These activated states are tentatively attributed to certain intermolecular modes of vibration in aggregates. Specifically, they fit the model of molecular torsional oscillation of two and three parallel-sheet arrangements. On the basis of these findings, we propose that the first Ea (or [Formula: see text]) is the fundamental librational frequency of the dimer and the second Ea (or [Formula: see text]) is that for the trimer.