Research

Electrosynthesis uses electrons as a potent, controllable, and traceless alternative to chemical oxidants or reductants. It typically offers a more sustainable alternative to conventional redox reactions, sometimes succeeding with better selectivity or unique reactions. Thermodynamics and kinetics at the solid-liquid interface can be accelerated by controlling potentials and current intensities, while electrochemistry can simplify purification and post-treatment processes.

Our philosophy particularly emphasizes understanding the synthesis of electro- and photo- acitive polymers from electrochemical approaches. Solid-phase electrosynthesis developed in our group can enable real-time monitoring of molecular growth while producing complex composition and sequence of monomers, coupling reactions, and ions within non-, d-π, and π-π* conjugated polymers. Recent information on our group's current research activities, which focus on solid-phase electrosynthesis, can be found in the group's publications, and a brief introduction to each example of recent projects is provided below.

Keywords: Solid-phase electrosynthesis, Iterative synthesis, Sequence-controlled synthesis,  precise synthesis, metallopolymer, polymer Monolayer, End-on polymers, polymer brush, Negative differential resistance effect, Organic mixed ionic-electronic transport, Memristor

(1) Solid-Phase Electrosynthesis (Electrochemical Iterative Synthesis, Precise Synthesis, Polymer Orientation)

We proposed the concept of solid-phase electrosynthesis, which simultaneously enables rapidly surface-initiated uniform electrosynthesis and unidirectional assembly of metallopolymers via kinetically accelerated and statistically allowed iterative growth.

Fig. 1 Solid-phase electrosynthesis.

Acc. Chem. Res. 2023, 56, 3694.

 (2) Vertically oriented conjugated metallopolymers as two-dimentional nanoarchitectures

Long-range ordered nanoarchitecture of polymers is hampered by kinetic and statistical restrictions during polymer synthesis and manipulation. We have reported the monolayer nanoarchitecture of long-range crystalline metallopolymers via kinetically accelerated and statistically allowed iterative growth, guided by a self-assembled monolayer with monitoring and defect-repair abilities.

Fig. 2 Nanoarchitectonics on electrosynthesis and assembly of conjugated metallopolymers.

Angew. Chem. Int. Ed. 2023, 135, e202311778. hot paper

(3) Sequence-Controlled Conductance and Memristive Functions of Metallopolymer Monolayers

Understanding how charge travels through sequence-controlled molecules has been a formidable challenge due to simultaneous requirements in well-controlled synthesis and well-manipulated orientation. We reported electrically driven simultaneous synthesis and crystallization as a general strategy to study the conductance of composition and sequence-controlled unioligomer and unipolymer monolayers. Our work demonstrated a promising way to release an ultra-rich variety of electrical parameters and optimize the functions and performances of multilevel resistive devices.

Fig. 3 Composition and sequence-controlled conductance of crystalline unimolecular monolayers.

Sci. Adv. 2023, 9, eadh0667.