RT Journal Article
T1 Mutual Monomer Orientation To Bias the Supramolecular Polymerization of [6]Helicenes and the Resulting Circularly Polarized Light and Spin Filtering Properties
A1 Rodríguez, Rafael
A1 Naranjo Calderón, Cristina
A1 Kumar, Anil
A1 Matozzo, Paola
A1 Das, Tapan Kumar
A1 Zhu, Qirong
A1 Vanthuyne, Nicolas
A1 Gómez Aspe, Rafael
A1 Naaman, Ron
A1 Sánchez Martín, Luis
A1 Crassous, Jeanne
AB 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 glum 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 glum 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.
PB American Chemical Society
SN 0002-7863
YR 2022
FD 2022
LK https://hdl.handle.net/20.500.14352/93169
UL https://hdl.handle.net/20.500.14352/93169
LA eng
NO Rodríguez, R.; Naranjo, C.; Kumar, A.; Matozzo, P.; Das, T. K.; Zhu, Q.; Vanthuyne, N.; Gómez, R.; Naaman, R.; Sánchez, L.; Crassous, J. Mutual Monomer Orientation To Bias the Supramolecular Polymerization of [6]Helicenes and the Resulting Circularly Polarized Light and Spin Filtering Properties. J. Am. Chem. Soc. 2022, 144, 7709-7719 DOI:10.1021/jacs.2c00556.
NO Ministerio de Ciencia, Innovación y Universidades (España)
NO Comunidad de Madrid
DS Docta Complutense
RD 9 abr 2025