Cooperative Self-Assembly Driven by Multiple Noncovalent Interactions: Investigating Molecular Origin and Reassessing Characterization

Cooperative interactions play a pivotal role in programmable supramolecular assembly. Emerging from a complex interplay of multiple noncovalent interactions, achieving cooperativity has largely relied on empirical knowledge. Its development as a rational design tool in molecular self-assembly requires a detailed characterization of the underlying interactions, which has hitherto been a challenge for assemblies that lack long-range order. We employ extensive one- and two-dimensional magic-angle-spinning (MAS) solid-state NMR spectroscopy to elucidate key structure-directing interactions in cooperatively bound aggregates of a perylene bisimide (PBI) chromophore. Analysis of H-1-C-13 cross-polarization heteronuclear correlation (CP-HETCOR) and H-1-H-1 double-quantum single-quantum (DQ-SQ) correlation spectra allow the identification of through-space H-1 center dot center dot center dot C-13 and H-1 center dot center dot center dot H-1 proximities in the assembled state and reveals the nature of molecular organization in the solid aggregates. Emergence of cooperativity from the synergistic interaction between a stronger pi-stacking and a weaker interstack hydrogen-bonding is elucidated. Finally, using a combination of optical absorption, circular dichroism, and high-resolution MAS NMR spectroscopy based titration experiments, we investigate the anomalous solvent-induced disassembly of aggregates. Our results highlight the disparity between two well-established approaches of characterizing cooperativity, using thermal and good solvent-induced disassembly. The anomaly is explained by elucidating the difference between two disassembly pathways.