title: Turning off the majority-rules effect in two-dimensional hierarchical chiral assembly by introducing a chiral mismatch.
abstract: Understanding the mechanism in chiral transmission from a single molecule to a supramolecular level is fundamentally important to decipher the nonlinear amplification effect in the two-dimensional (2D) chiral assembly process. In this contribution, we report on the dramatically different nonlinear amplification effect in the chiral co-adsorber induced homochiral assemblies constructed by a series of homologous achiral building blocks on the graphite surface under control of the majority-rules principle. Homologous hexagonal networks are formed for 5-(benzyloxy)-isophthalic acid (BIC) derivatives with different alkyl lengths. While globally homochiral monolayers of BIC-C6 or BIC-C16 can be obtained by using a mixture of chiral co-adsorber 2-octanol with a small enantiomeric excess, such majority-rules principle based nonlinear chiral amplification is inoperative for the assembly of BIC-C10. Molecular mechanistic analysis indicates that BIC-C10 assembly can accommodate a chiral mismatched motif to form long-range ordered but short-range disordered crystalline networks, leading to the co-adsorption of enantiomers without enantioselectivity. The present results shed important insights into the significance of chirality mismatch during chiral transmission and benefit the understanding of chiral communication in a surface monolayer.
authors.affiliation: Key Laboratory of Molecular Nanostructure and Nanotechnology and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, P.R. China and University of Chinese Academy of Sciences, Beijing 100049, P.R. China. wangd@iccas.ac.cn wanlijun@iccas.ac.cn.
authors.forename: Shu-Ying
authors.initials: SY
authors.lastname: Li
authors.affiliation: Key Laboratory of Molecular Nanostructure and Nanotechnology and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, P.R. China.
authors.forename: Ting
authors.initials: T
authors.lastname: Chen
authors.affiliation: Key Laboratory of Molecular Nanostructure and Nanotechnology and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, P.R. China and University of Chinese Academy of Sciences, Beijing 100049, P.R. China. wangd@iccas.ac.cn wanlijun@iccas.ac.cn.
authors.forename: Lin
authors.initials: L
authors.lastname: Wang
authors.affiliation: Key Laboratory of Molecular Nanostructure and Nanotechnology and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, P.R. China.
authors.forename: Dong
authors.initials: D
authors.lastname: Wang
authors.affiliation: Key Laboratory of Molecular Nanostructure and Nanotechnology and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, P.R. China.
authors.forename: Li-Jun
authors.initials: LJ
authors.lastname: Wan