Conformational switching modulates excited-state pathways in a cofacial perylene dimer

Controlling excited-state pathways in supramolecular chromophore assemblies is key to designing next-generation optoelectronic and photonic materials. Here we elucidate the conformation-dependent photophysics of a flexible perylene diimide (PDI) dimer, valPDI₂, which undergoes reversible solvent-driven switching between two distinct dimer geometries, within the same structure. Exciton-coupling calculations and ultrafast spectroscopy show that in chloroform the dimer adopts an open, weakly coupled geometry that supports slow, partial excimer formation due to structural inhomogeneity within the excited state potential. In contrast, in polar DMSO/water the dimer collapses into a cofacial stacked conformer that enables barrierless, sub-200 femtosecond excimer formation, a subset of which forms a multiexciton state over tens of picoseconds. Half-broadband 2D electronic spectroscopy reveals conformation-dependent vibrational coherences, with nuclear wavepacket motion along the π-stacking coordinate promoting vibrationally coherent excimer formation in the closed conformer. These findings demonstrate that environmentally driven conformational control offers a powerful non-covalent strategy to modulate excimer and multiexciton dynamics in PDI assemblies. More broadly, they establish supramolecular switching as a general design principle for tuning excited-state behaviour in flexible organic chromophore arrays, with implications for the development of responsive optoelectronic and energy-conversion materials.