Monolayer nanoarchitecture of crystalline metallopolymers by electrochemical iterative growth

The assembly of oriented molecular nanoarchitecture by controlled manipulation on a molecule-by-molecule basis is desirable for molecular materials and electronics. However, this nanoarchitecture of polymers is hampered by kinetic and statistical restrictions during polymer synthesis and manipulation. Here, we report the monolayer nanoarchitecture of long-range crystalline metallopolymers in vertical arrays, with heights ranging from 2 to 30 nm on conductive substrates, via kinetically accelerated and statistically allowed iterative growth, guided by a self-assembled monolayer with monitoring and defect-repair abilities. The monolayer shows a surface roughness of 0.65 nm, a theoretically highest density of 0.79 chains/nm2, and superior tailoring in conductance and electrocatalysts as a function of height with very low decay constants in the electron transport of 0.063 nm−1. Highly controlled synthesis for engineering standard functional polymer monolayers with a uniformity in single monomer precise can present superior structure and function in contrast to conventional SAMs based on small molecules.