The synthesis and self-assembling features of the N-annulated perylene diimide (NPBI) 1 in different solvents are reported. Compound 1 possesses two chiral linkers, derived from (S)-(+)-alaninol, that connect the central aromatic NPBI segment and the peripheral trialkoxybenzamide units. The Ala-based linker has been demonstrated to strongly favor the formation of intramolecularly H-bonded seven-membered pseudocycles. NPBI 1 shows a strong tendency to self-assemble even in a good solvent like CHCl3 and the formation of chiral dimers is detected in this good solvent. Both experimental techniques and theoretical calculations reveal that the intramolecular H-bonded pseudocycles are very robust and the formation of chiral dimers is driven by the π-stacking of two units of the NPBI core. Unexpectedly, an efficient transfer of the asymmetry of the point chirality at the linker to the aromatic moiety is observed in the molecularly dissolved state. Changing the solvent to more apolar methylcyclohexane modifies the self-assembly process and the formation of chiral supramolecular polymers is detected. The supramolecular polymerization of 1 is demonstrated to follow an isodesmic mechanism unlike previous referable systems. In the formation of the supramolecular polymers of 1, the combination of experimental and computational data indicates that the H-bonded pseudocycles are also present in the aggregated state and the rope-like, columnar aggregates formed by the self-assembly of 1 rely on the π-stacking of the NPBI backbones.
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