title: The origin of isotope-induced helical-sense bias in supramolecular polymers of benzene-1,3,5-tricarboxamides.
abstract: The molecular origin of the isotope-induced diastereomeric enrichment in helical supramolecular polymers consisting of trialkylbenzene-1,3,5-tricarboxamides (BTAs) is studied using plane-wave DFT calculations. We demonstrate that the creation of a chiral center at the α-position of the alkyl chains of a BTA by H-D exchange leads to a small but notable preference for the formation of supramolecular hydrogen bonded structures with a particular helicity. The bias for one helical sense preference is caused by the orientation of the vibrational eigenmodes of the C-H and C-D stretching frequencies at the chiral center and by hyperconjugative destabilization of the anti C-H orbital.
authors.affiliation: Institute for Complex Molecular Systems, Eindhoven University of Technology, P. O. Box 513, 5600 MB, Eindhoven, The Netherlands.
authors.forename: Ivo A W
authors.initials: IA
authors.lastname: Filot
authors.forename: Anja R A
authors.initials: AR
authors.lastname: Palmans
authors.forename: Peter A J
authors.initials: PA
authors.lastname: Hilbers
authors.forename: Emiel J M
authors.initials: EJ
authors.lastname: Hensen
authors.forename: Tom F A
authors.initials: TF
authors.lastname: de Greef
authors.forename: Evgeny A
authors.initials: EA
authors.lastname: Pidko
mesh_terms: D001549:Benzamides / Q000737:chemistry*; D003903:Deuterium / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D011108:Polymers / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D001549:Benzamides; D011108:Polymers; C558700:benzene-1,3,5-tricarboxamide; D006859:Hydrogen; D003903:Deuterium