RT Journal Article
T1 Enantiomerically pure helical bilayer nanographenes: a straightforward chemical approach
A1 Izquierdo García, Patricia
A1 Fernández García, Jesús Manuel
A1 Perles, Josefina
A1 Martín León, Nazario
AB The semiconductor properties of nanosized graphene fragments, known as molecular nanographenes, position them as exceptional candidates for next-generation optoelectronics. In addition to their remarkable optical and electronic features, chiral nanographenes exhibit high dissymmetry factors in circular dichroism and circularly polarized luminescence measurements. However, the synthesis of enantiomerically pure nanographenes remains a significant challenge. Typically, these materials are synthesized in their racemic form, followed by separation of the enantiomers using high-performance liquid chromatography (HPLC). While effective, this method often requires expensive instrumentation, extensive optimization of separation conditions, and typically yields analytical quantities of the desired samples. An alternative approach is the enantioselective synthesis of chiral molecular nanographenes; however, to date, only two examples have been documented in the literature. In this work, we present a straightforward chemical method for the chiral resolution of helical bilayer nanographenes. This approach enables the effective and scalable preparation of enantiomerically pure nanographenes while avoiding the need for HPLC. The incorporation of a BINOL core into the polyarene precursor facilitates the separation of diastereomers through esterification with enantiomerically pure camphorsulfonyl chloride. Following the separation of the diastereomers by standard chromatographic column, the hydrolysis of the camphorsulfonyl group yields enantiomerically pure nanographene precursors. The subsequent graphitization, achieved through the Scholl reaction, occurs in an enantiospecific manner and with the concomitant formation of a furan ring and a heterohelicene moiety. The absolute configurations of the final enantiomers, P-oxa[9]HBNG and M-oxa[9]HBNG, have been determined using X-ray diffraction. Additionally, electrochemical, photophysical, and chiroptical properties have been thoroughly evaluated.
PB ACS
SN 0002-7863
YR 2024
FD 2024-12-06
LK https://hdl.handle.net/20.500.14352/120383
UL https://hdl.handle.net/20.500.14352/120383
LA eng
NO Izquierdo-García, P.; Fernández-García, J. M.; Perles, J.; Martín, N. Enantiomerically Pure Helical Bilayer Nanographenes: A Straightforward Chemical Approach. J. Am. Chem. Soc. 2024, 146 (50), 34943–34949. https://doi.org/10.1021/jacs.4c14544.
NO P.I.-G., J.M.F.-G. and N.M. acknowledge financial support from the Spanish MICIN (project PID2020-114653RB I00), they also acknowledge financial support from the ERC (SyG TOMATTO ERC-2020-951224) and from the “(MAD2D-CM)-UCM” project funded by Comunidad de Madrid, by the Recovery, Transformation and Resilience Plan, and by NextGenerationEU from the European Union.
NO Ministerio de Ciencia, Innovación y Universidades (España)
NO Consejo Europeo de Investigación (UE)
NO Comunidad de Madrid
DS Docta Complutense
RD 20 mar 2026