The unique self‐assembling features of N‐annulated perylene bisimides (PBIs) 1 and 2 are reported. The stability of the aggregates of diester 1, in which no H‐bonding interactions are operative, corroborates the significance of long‐range van der Waals and dipole–dipole electrostatic interactions in the construction of stable supramolecular assemblies. The incorporation of amide functional groups within the N‐annulated PBI in 2 stimulates pathway differentiation to achieve up to three J‐type aggregates and a fourth H‐type aggregate depending on the experimental conditions. The results presented demonstrate unprecedented levels of control over synthetic supramolecular self‐assembly and the rich differentiation that N‐annulated PBIs exhibit, opening the door to new, complex, functional supramolecular materials.

Studies were carried out on the hierarchical self-assembly versus pathway complexity of N-annulated perylenes 1-3, which differ only in the nature of the linking groups connecting the perylene core and the side alkoxy chains. Despite the structural similarity, compounds 1 and 2 exhibit noticeable differences in their self-assembly. Whereas 1 forms an off-pathway aggregate I that converts over time (or by addition of seeds) into the thermodynamic, on-pathway product, 2 undergoes a hierarchical process in which the kinetically trapped monomer species does not lead to a kinetically controlled supramolecular growth. Finally, compound 3, which lacks the amide groups, is unable to self-assemble under identical experimental conditions and highlights the key relevance of the amide groups and their position to govern the self-assembly pathways.

The three-domain cooperative supramolecular polymerization of 1, together with the lag time in which the monomeric species remains inactive, allows seeded supramolecular polymerization to be performed. The kinetic experiments demonstrate that only seeds based on the intermediate aggregate are able to propagate the supramolecular polymerization of 1 from their active sites. The results presented herein constitute a new example of kinetically controlled supramolecular systems and contribute to expanding knowledge about the structural requirements of a self-assembling molecule to experience seeded supramolecular polymerization.

The formation of helical structures through the supramolecular polymerization of a variety of self‐assembling units is reviewed. These scaffolds are usually obtained by efficient transfer or amplification of chirality phenomena, in which the starting self‐assembling molecules possess different elements of asymmetry, such as point or axial chirality. Relevant examples of helical supramolecular structures investigated under thermodynamic control are reviewed, and the helical outcome of remarkable examples of chiral entities obtained through kinetic control are also highlighted. Finally, selected examples of flexible macroscopic chirality and catalysis are described to illustrate the applicability of helical aggregates.

A complete series of experimental and theoretical investigations on the supramolecular polymerization of chiral (1 and 2) and achiral (3) oligo­(phenylene ethynylene) tricarboxamides (OPE-TAs) is reported. The performance of seargents-and-soldiers (SaS) and majority rules (MR) experiments has allowed deriving a full set of thermodynamic parameters, including the helix reversal penalty (HRP) and the mismatch penalty (MMP). The results described illustrate the influence exerted by the number of stereogenic centers per monomeric unit and the temperature on the chiral amplification phenomenon. While the HRP decreases upon decreasing the number of chiral side chains, the MMP follows an opposite trend. The experimental trend observed in MR experiments contrasts with that reported for benzenetricarboxamides (BTAs), for which the chiral amplification ability increases by lowering the number of stereogenic centers or increasing the temperature. Theoretical calculations predict that the rotational angle between adjacent monomeric units in the stack (ca. 18°) gradually decreases when decreasing the number of branched chiral side chains and leads to higher MMP values, in good accord with the experimental trend. The reduction of the rotational angle gives rise to less efficient H-bonding interactions between the peripheral amide functional groups and is suggested to provoke a decrease of the HRP as experimentally observed. In BTAs, increasing the number of stereogenic centers per monomeric unit results in a negligible change of the rotation angle between adjacent units (ca. 65°), and, consequently, the steric bulk increases with the number of chiral side chains, leading to higher MMP values. The data presented herein contribute to shed light on the parameters controlling the transfer and amplification of chirality processes in supramolecular polymers, highlighting the enormous influence exerted by the size of the self-assembling unit on the final helical outcome.

Herein, the impact of alkyl bridge length is unraveled on the self‐assembly of N‐annulated perylenetetracarboxamides 1–4 that cooperatively form supramolecular polymers. Spectroscopic studies in different solvents as media for the self‐assembly demonstrate the impact that the length of the bridge separating the two amide groups of compounds 1–4 exerts on the supramolecular polymerization process: i) in MCH/Tol (8/2), compounds 1–3 exhibit a consecutive process that, however, it is not operative for 4; ii) the presence of three methylene units in 2, which can induce a parallel distribution of the amide groups, notably decreases the stability of the corresponding aggregates in Tol; iii) increasing the spacer length accelerates the conversion of the metastable, intramolecularly H‐bonded monomeric species, which prevents to develop seeded supramolecular polymerizations; iv) the presence of a spacer with five methylene units in 4 hinders the formation of the corresponding 10‐membered pseudo‐cycle; and v) only the higher relative stability of the inactivated monomeric species of 1 enables pathway complexity, with a kinetically controlled self‐assembly to yield nanoparticles and a thermodynamically controlled supramolecular polymerization to achieve fibrillar structures. The results presented herein expand the knowledge on the structure/property relationship for self‐assembling units to provide pathway complexity and to bias the kinetics and stability of the supramolecular aggregates.

The unique self‐assembling features of N‐annulated perylene bisimides (PBIs) 1 and 2 are reported. The stability of the aggregates of diester 1, in which no H‐bonding interactions are operative, corroborates the significance of long‐range van der Waals and dipole–dipole electrostatic interactions in the construction of stable supramolecular assemblies. The incorporation of amide functional groups within the N‐annulated PBI in 2 stimulates pathway differentiation to achieve up to three J‐type aggregates and a fourth H‐type aggregate depending on the experimental conditions. The results presented demonstrate unprecedented levels of control over synthetic supramolecular self‐assembly and the rich differentiation that N‐annulated PBIs exhibit, opening the door to new, complex, functional supramolecular materials.

T-Shaped 2H-benzo[d][1,2,3]triazole derivatives have been synthesized by Sonogashira coupling reactions under microwave irradiation.