Solvent Polarity Independent Symmetry-Breaking Charge Separation in a Slip-Stacked Covalent Terrylene Monoimide Dimer

The design of organic materials capable of efficient photoinduced charge separation in low-polarity environments is a critical challenge for advancing organic photovoltaics. Symmetry-breaking charge separation (SB-CS) offers a promising route to efficient charge separation with minimal energy loss; however, in conventional organic materials this process typically relies on polar solvents to stabilize the charge-separated state. Here, we investigate a slip-stacked terrylene monoimide dimer (<b>TMI</b>_<b>2</b>) engineered with intrinsic electronic asymmetry to circumvent this limitation. We demonstrate through a comprehensive suite of ultrafast spectroscopic techniques that <b>TMI</b>_<b>2</b> undergoes remarkably efficient SB-CS regardless of solvent polarity enabled by the permanent dipole moment of <b>TMI</b> and the accessible intramolecular charge-transfer (ICT) character of its monomer units. Furthermore, analysis of vibronic coherences reveals that the initial state mixing is actively driven by a 193 cm^-1 intermolecular mode, while the final SB-CS state is marked by a distinct vibrational fingerprint of the radical ion pair product. Our findings reveal how the intrinsic electronic asymmetry of the <b>TMI</b> monomers that constitute <b>TMI</b>_<b>2</b> creates an efficient charge separation pathway that precludes the need for external stabilization from a polar solvent. This work establishes a powerful molecular design principle for leveraging intrinsic monomeric asymmetry to achieve efficient charge separation in low-dielectric environments, with significant implications for the development of next-generation organic optoelectronic materials.