Within the field of supramolecular polymers, chiral supramolecular polymers are an excellent benchmark to generate helical structures that can clarify the origin of homochirality in Nature or to find out new exciting functionalities of organic materials.

We report on the synthesis and self-assembly of 2,15- and 4,13-disubstituted carbo[6]helicenes 1 and 2 bearing 3,4,5-tridodecyloxybenzamide groups. The self-assembly of these [6]helicenes is strongly influenced by the substitution pattern in the helicene core that affects the mutual orientation of the monomeric units in the aggregated form. Thus, the 2,15-substituted derivative 1 undergoes an isodesmic supramolecular polymerization forming globular nanoparticles that maintain circularly polarized light (CPL) with g_lum values as high as 2 × 10^–2. Unlike carbo[6]helicene 1, the 4,13-substituted derivative 2 follows a cooperative mechanism generating helical one-dimensional fibers. As a result of this helical organization, [6]helicene 2 exhibits a unique modification in its ECD spectral pattern showing sign inversion at low energy, accompanied by a sign change of the CPL with g_lum values of 1.2 × 10^–3, thus unveiling an example of CPL inversion upon supramolecular polymerization. These helical supramolecular structures with high chiroptical activity, when deposited on conductive surfaces, revealed highly efficient electron-spin filtering abilities, with electron spin polarizations up to 80% for 1 and 60% for 2, as measured by magnetic conducting atomic force microscopy.

Herein, the synthesis and self‐assembling features of N‐heterotriangulenes 1–3 decorated in their periphery with 3,4,5‐trialkoxy‐N‐(alkoxy)benzamide moieties that enable kinetic control of the supramolecular polymerization process are described. The selection of an appropriate solvent results in a tunable energy landscape in which the relative energy of the different monomeric or aggregated species can be regulated. Thus, in a methylcyclohexane/toluene (MCH/Tol) mixture, intramolecular hydrogen‐bonding interactions in the peripheral side units favor the formation of metastable inactivated monomers that evolve with time at precise conditions of concentration and temperature. A pathway complexity in the supramolecular polymerization of 1–3 cannot be determined in MCH/Tol mixtures but, importantly, this situation changes by using CCl₄. In this solvent, the off‐pathway product is a face‐to‐face H‐type aggregate and the on‐pathway product is the slipped face‐to‐face J‐type aggregate. The autocatalytic transformation of the metastable monomeric units, as well as the two competing off‐ and on‐pathway aggregates allow the realization of seeded and living supramolecular polymerizations. Interestingly, the presence of chiral, branched side chains in chiral (S)‐2 noticeably retards the kinetics of the investigated transformations. This work brings to light the relevance of controlling the pathway complexity in self‐assembling units and opens new avenues for the investigation of complex and functional supramolecular structures.