Substrate-Directed Chiral Selectivity of Molecular Self-Assembled and Covalent Structures

•On Ag(111) and Ag(100) held at 120 K, intact molecules self-assemble into the homochiral and racemic structures, respectively.•Organometallic and covalent polymers are composed of homochiral molecules on Ag(111).•Poor chiral selectivity is found for the organometallic and covalent polymers on Ag(100).•Substrate reactivity and lattice symmetry should be responsible for the different selectivity of products on Ag(111) and Ag(100) according to the comparative experiments.