Unravel Excited State Chirality Dynamics During Symmetry-Breaking Charge Separation

• • SB-CS in chiral perylenediimide (Cy-PDI 2) occurs within 88 ps in THF, as confirmed by transient absorption, enabling ultrafast charge separation for photovoltaic applications. • • Time-resolved circularly polarized luminescence reveals a 10-fold (one order of magnitude) amplification of the emission dissymmetry factor g_lum(t) during SB-CS, indicating enhanced excited-state chirality. • • The SB-CS process is strongly quenched in toluene (TOL) compared to THF, demonstrating solvent-dependent control over charge separation and chirality dynamics. • • The combination of TRCPL and TA spectroscopy provides a novel methodology to directly probe excited-state chirality dynamics, offering a tool for designing chiral optoelectronic materials.