Supramolecular polymerization and bulk properties relationship in ester-functionalized N-annulated perylenediimides

The synthesis of a series of N-annulated perylenediimides (NPDIs) 1-4 with an ester group and an alkyl spacer of different length in the peripheral chains was carried out, and the influence of the side chain architecture on the self-assembly, both in solution and in the solid state, was investigated. Solution studies evidenced that the carbonyl group plays a key role in the supramolecular organization of these derivatives, changing from an H-type isodesmic polymerization (4) to a J-type cooperative process as the spacer length decreases (1-3). On the other hand, bulk assays revealed an odd-even effect that correlates with the length of the alkyl spacer. Whereas the odd-spaced derivatives (2 and 4) organize in a disordered columnar hexagonal fashion, the even-spaced ones (1 and 3) show the formation of multiple crystalline (and liquid crystalline) structures. The results presented herein highlight the importance of side chain functionalization in the design of building blocks for in-solution and bulk purposes.