Metal-dependent Excited-State Dynamics and Charge Transport in Copper and Silver Corrole-Fullerene Dyads

We report a class of covalently linked metallocorrole-fullerene dyads that integrate molecular-level design with device-relevant charge transport. Copper- and silver-corrole units are fused to C60 via a pyrrolidine linker. SC-XRD of the silver dyad reveals unusually short C60···Ag(III) contacts (2.96 Å), evidencing strong donor-acceptor coupling. Steady-state spectra show fulleropyrrolidine absorptions and subtle Soret/Q-band shifts upon conjugation. DFT reveals a HOMO delocalized over the corrole-phenylene framework and distinct LUMO distributions, with spin-dependent localization in the copper dyad and fullerene localization in the silver dyad. Electrochemistry resolves metallocorrole oxidations and fullerene reductions, while Rehm-Weller analysis indicates feasible photoinduced charge separation. Ultrafast transient absorption uncovers a heavy-atom-assisted route: rapid singlet-singlet energy transfers to the fulleropyrrolidine followed by accelerated intersystem crossing, with no spectroscopic signature of a charge-separated state on the fs-ns window. Indication of charge separation is instead found in the ns-μs time window for the copper dyad. Solid-state space-charge-limited current measurements reveal complementary transport behavior: the silver dyad functions as a high-mobility p-type material, whereas the copper dyad exhibits reasonable electron and hole mobility, which can be correlated to the energetic landscape of these molecules. Together, these results establish metallocorrole-fullerene dyads as tunable platforms that bridge excited-state dynamics with long-range charge transport for organic optoelectronic applications.