%0 Journal Article
%A Naranjo Calderón, Cristina
%A Doncel-Giménez, Azahara
%A Gómez Aspe, Rafael
%A Aragó, Juan
%A Ortí, Enrique
%A Sánchez Martín, Luis
%T Solvent-dependent self-assembly of N-annulated perylene diimides. From dimers to supramolecular polymers
%D 2023
%U https://hdl.handle.net/20.500.14352/105791
%X 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-basedlinker 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 techniquesand theoretical calculations reveal that the intramolecular H-bonded pseudocycles are very robust andthe formation of chiral dimers is driven by the p-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 isobserved in the molecularly dissolved state. Changing the solvent to more apolar methylcyclohexanemodifies the self-assembly process and the formation of chiral supramolecular polymers is detected. Thesupramolecular polymerization of 1 is demonstrated to follow an isodesmic mechanism unlike previousreferable systems. In the formation of the supramolecular polymers of 1, the combination ofexperimental and computational data indicates that the H-bonded pseudocycles are also present in theaggregated state and the rope-like, columnar aggregates formed by the self-assembly of 1 rely on thep-stacking of the NPBI backbones.
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