Nanoarchitectonics on Electrosynthesis and Assembly of Conjugated Metallopolymers.

In contrast to edge-on and face-on orientations, end-on uniaxial conjugated polymers have the theoretical possibility of providing a macroscopic crystalline film. However, their fabrication is insurmountable due to sluggishly thermodynamic equilibrium states. Herein, we report the programmatic pathway to fabricate nanoarchitectonics on end-on uniaxial conjugated metallopolymers by surface-initiated simultaneous electrosynthesis and assembly. Self-assembled monolayer (SAM) with bottom-up oriented electroactive molecules as a temple allows orientation, stacking, and reactive addition of monomers triggered by switching alternative redox reactions as well as crystallization of small molecules. Repeating the same reaction can repair the unreactive site on the SAM and dynamically and statistically ensure maximum iterative coverage with ideal linear coefficients between optical or electrical responses and iterative times. The resulting nanoarchitectonics on uniaxially assembled end-on polymers over centimeter-sized areas have a subnanometer-uniform morphology and exhibit ultrahigh modulus as well as an inorganic indium tin oxides and the highest conductance among conjugated molecular monolayers. Their memristive devices provide quantitative electrical and optical responses as a function of molecular length, bias, and iterative junctions. Precise processing of nanoarchitectonics as an electrically assisted assembly or printing technique can present sophisticated optoelectric functions and dimensional batch-to-batch consistency for micro-sized organic materials and electronics.