title: "Majority-rules" operative in chiral columnar stacks of C3-symmetrical molecules.
abstract: C(3)-symmetrical disks 1, preorganized by acylated 2,2'-bipyridine-3,3'-diamine moieties and decorated with nine identical chiral, lipophilic tails, aggregate into a dynamic helix in apolar solvents. The aggregates, previously shown to be governed by the "sergeants-and-soldiers" principle when mixed with achiral analogues, are now also revealed to obey the "majority-rules" effect, a phenomenon not earlier observed in nonpolymers. Our experimental circular dichroism data can be accurately described with a recently developed theory. A fit of the theory to the experimental results shows that the mismatch penalty, i.e., the free energy of a monomer present in a helix of its nonpreferred screw sense (0.94 kJ/mol), is about 8 times lower than the penalty for a helix reversal (7.8 kJ/mol). This corresponds well to our vision of the supramolecular architecture of the disks.
authors.affiliation: Laboratory of Macromolecular and Organic Chemistry, Technische Universiteit Eindhoven, P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
authors.forename: Jeroen
authors.initials: J
authors.lastname: van Gestel
authors.forename: Anja R A
authors.initials: AR
authors.lastname: Palmans
authors.forename: Bram
authors.initials: B
authors.lastname: Titulaer
authors.forename: Jef A J M
authors.initials: JA
authors.lastname: Vekemans
authors.forename: E W
authors.initials: EW
authors.lastname: Meijer