Extended enantiopure ortho-phenylene ethylene (o-OPE)-based helical systems as scaffolds for supramolecular architectures: a study of chiroptical response and its connection to the CISS effect

Year: 2021

Authors: Ortuso AM., Reinè P., Resa S., de Cienfuegos LA., Blanco V., Paredes JM., Mota AJ., Mazzeo G., Abbate S., Ugalde JM., Mujica V., Longhi G., Miguel D., Cuerva JM.

Autors Affiliation: Univ Granada UGR, Unidad Excelencia Quim UEQ, Dept Organ Chem, Fac Sci, ES-18071 Granada, Spain; UGR UEQ, Fac Pharm, Dept Phys Chem, Dubai, U Arab Emirates; UGR UEQ, Dept Inorgan Chem, Fac Sci, Dubai, U Arab Emirates; Univ Brescia, Dept Mol & Translat Med, Brescia, Italy; Ist Nazl Ottica CNR, Brescia Res Unit, Via Branze 45, I-25123 Brescia, Italy; Euskal Herriko Unibertsitatea, Kimika Fak, PK 1072, Donostia San Sebastian 20080, Euskadi, Spain; Univ Arizona, Sch Mol Sci, Tempe, AZ 85287 USA.

Abstract: A novel synthetic strategy based on a bifunctional stapled chiral nucleus from which segments of different lengths can be added to both ends of o-phenylene ethynylenes (o-OPEs) has been developed to obtain a new type of foldamer and a novel chiral Pd2L2 metallacycle. For the first time, an enantiopure fully conjugated helical foldamer having 14 phenyl rings and 13 alkynes is reported. The folded structure has four complete loops and is able to host three Ag(i) cations in their cavity with high binding constants. The complete photophysical and chiroptical (ECD, CPL and VCD) characterization of these foldamers has shown that these molecules show intense chiroptical responses with dissymmetry ratios in the range of 10(-2). Theoretical modeling of these systems reveals the origin of these remarkable responses and points out a potential connection with the chiral induced spin selectivity (CISS) effect. The magnetic dipole moment is proposed as a key physical variable connecting the chiroptical properties and CISS-based spin filtering properties observed in chiral compounds.

Journal/Review: ORGANIC CHEMISTRY FRONTIERS

Volume: 8 (18)      Pages from: 5071  to: 5086

More Information: We thank the Ministerio de Economia y Competitividad (CTQ2017-85454-C2-1-P), Ministerio de Ciencia en Innovacion (PID2020-113059GB-C21) and Junta de Andalucia (P20_00162) (Spain) for funding and P. R. and A. O. G. also for FPU contracts. We also thank the UGR CSIRC for access to computational facilities. We also thank Big&Open Data Innovation Laboratory (BODaI-Lab), University of Brescia, granted by Fondazione Cariplo and Regione Lombardia, for access to resources of Computing Center CINECA (Bologna), Italy. Support from the Italian MIUR (grant N. 2017A4XRCA) is also acknowledged. VM acknowledges a Fellowship from Ikerbasque, the Basque Foundation for Science.
KeyWords: Circularly-polarized Luminescence; Chiral Molecules; Spin Selectivity; O-opes; Foldamer; Transport; Binding; Sense; Bias; Transmission
DOI: 10.1039/d1qo00822f

Citations: 16
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