Intersystem crossing pathways in [5]-, [7]-, and [9]cycloparaphenylenes

We analyze the energetics and internal conversion dynamics of singlet and triplet manifolds to identify the possible intersystem crossing pathways in odd-numbered [n]cycloparaphenylenes ([n]CPPs, n = 5, 7, and 9). Quantum wavepacket propagation calculations within the linear vibronic coupling framework suggest that both [5]- and [7]CPPs rapidly relax to S2 upon populating “bright” higher singlet excited states. The S2–S1 energy decreases with the increase in CPP size, and hence, [9]CPP exhibits a faster S2 → S1 internal conversion decay. Higher triplet states act as receiver states for the intersystem crossing happening either via S1 or S2. The wavepacket evolving on the receiver triplet state would decay to lower states via multiple conical intersections and reach T1. The estimated size-dependent fluorescence and emission energies are in good accord with the experiment.