Mutual Monomer Orientation To Bias the Supramolecular Polymerization of 6Helicenes and the Resulting Circularly Polarized Light and Spin Filtering Properties

High Resolution Image Download MS PowerPoint Slide We report on the synthesis and self-assembly of 2,15- and 4,13-disubstituted carbo6helicenes 1 and 2 bearing 3,4,5-tridodecyloxybenzamide groups. The self-assembly of these 6helicenes 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 carbo6helicene 1, the 4,13-substituted derivative 2 follows a cooperative mechanism generating helical one-dimensional fibers. As a result of this helical organization, 6helicene 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.