(Octakis-(3,6-di-tert-butyl-9H-carbazole)phthalocyaninato)cobalt(II) (CoPc(Carb)8) was synthesized as a donor platform for coordination-driven self-assembly with 1-N-methyl-2-(pyridin-4-yl)pyrrolidino[3′,4’:1,2][60]fullerene (PyC60) and 4-(10-phenylanthracen-9-yl)pyridine. The formation of 1:1 coordination complexes (dyads) was confirmed by spectroscopic techniques (ultraviolet–visible (UV–vis), fluorescence, IR, MALDI-TOF), chemical thermodynamics and kinetics, and density functional theory (DFT) calculations. A model study with pyridine revealed the formation of both 1:1 and 1:2 complexes. DFT calculations were performed to determine the bonding energies and frontier orbital energies of CoPc(Carb)8 and its dyads. Similar highest occupied molecular orbital (HOMO) energies of CoPc(Carb)8 and its dyads result from their comparable electronic structures, while the variation in lowest unoccupied molecular orbital (LUMO) energies arises from differences in orbital composition, with contributions from the phthalocyanine core’s nonmetallic atoms and the cobalt 3dyz orbital. To evaluate the influence of carbazole substituents, analogous dyads based on (octakis(3,5-di-tert-butylphenoxy)phthalocyaninato)cobalt(II) (CoPc(3,5-tBuPhO)8) were investigated. The combination of quantum chemical calculations and the ultrafast femtosecond transient absorption spectroscopy method has allowed to discover and study the charge-separated states such as PyC60•– −CoPc(Carb)8•+ and PyC60•– −CoPc(3,5-tBuPhO)8•+, with lifetimes of 90.7 and >500 ps, respectively, in toluene. These findings enhance the understanding of cobalt(II) phthalocyanine-based donor–acceptor systems and inform the design of materials for photovoltaic applications.
