Dynamic control over supramolecular handedness by selecting chiral induction pathways at the solution-solid interface.
A dominant theme within the research on two-dimensional chirality is the sergeant-soldiers principle, wherein a small fraction of chiral molecules (sergeants) is used to skew the handedness of achiral molecules (soldiers) to generate a homochiral surface. Here, we have combined the sergeant-soldiers principle with temperature-dependent molecular self-assembly to unravel a peculiar chiral amplification mechanism at the solution-solid interface in which, depending on the concentration of a sergeant-soldiers solution, the majority handedness of the system can either be amplified or entirely reversed after an annealing step, furnishing a homochiral surface. Two discrete pathways that affect different stages of two-dimensional crystal growth are invoked for rationalizing this phenomenon and we present a set of experiments where the access to each pathway can be precisely controlled. These results demonstrate that a detailed understanding of subtle intermolecular and interfacial interactions can be used to induce drastic changes in the handedness of a supramolecular network.
Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001, Leuven, Belgium.
Yuan
Y
Fang
Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001, Leuven, Belgium.
Elke
E
Ghijsens
Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001, Leuven, Belgium.
Oleksandr
O
Ivasenko
Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001, Leuven, Belgium.
Hai
H
Cao
Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
Aya
A
Noguchi
Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001, Leuven, Belgium.
Kunal S
KS
Mali
Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.|Department of Applied Chemistry, School of Science and Technology, Meiji University, 1-1-1 Higashimita, Tama-ku, Kawasaki, 214-8571, Japan.
Kazukuni
K
Tahara
Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
Yoshito
Y
Tobe
Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001, Leuven, Belgium.
Steven
S
De Feyter