Modulating theCharge Transfer Coupling in Boron-DipyrrometheneHomodimers by π‑Bridge Units

To mimic the excitation energy conversion mechanisms observed in natural light-harvesting systems, we have extensively investigated photoinduced symmetry-breaking charge separations (SBCSs) in various multichromophoric model systems have been extensively investigated. However, designing multichromophoric model systems capable of simultaneously achieving ultrafast and complete SBCS remains a significant challenge. In this study, we employed benzene, thiophene, and furan as π-bridges to develop a series of boron dipyrromethene (BODIPY) homodimers. Spectral analysis, together with an estimation of the π-bridge-dependent charge transfer (CT) coupling using the fragment charge difference method, reveals that π-bridge units with different electron-donating abilities can effectively modulate the CT coupling between chromophores. Notably, the furan-based π-bridge, exhibiting the most pronounced electron-donating character, facilitates symmetry-breaking charge transfer (SBCT), i.e., excimer formation with a time constant of about 12 ps in weak polar toluene. Furthermore, a dramatic increase in the SBCS rate constant was observed in highly polar acetonitrile, improving from 60.4 ps for the benzene-bridged homodimer to 2.9 ps for the furan-bridged counterpart. These findings underscore the potential of π-bridge units in tuning the photophysical properties of covalent molecular aggregates by optimizing such systems for specific applications such as organic photovoltaics and photocatalysis.