Molecularly Imprinted Polymer for Selective Electrosynthesis of Biphenols

Abstract

Molecularly imprinted polymers (MIPs) have been widely studied for sensing and separation of compounds selectively. These artificial biomimicking recognition units are highly sensitive and selective to target analytes. Electrochemical preparation of MIPs offers advantages including ease of preparation as well as control over the polymer nucleation and growth, thickness, and film morphology. Moreover, it is possible to follow the formation of cavities electrochemically through the gate effect. Few reports have focussed on selective catalysis by using MIPs. However, the application of these MIPs in the field of electrocatalysis remains unexplored and, therefore, there is a large research scope in this domain.Biphenols are structural motifs of several molecules in nature and for many drugs. They are efficient ligands for catalytic systems and are highly stable under electrochemical condition. In particular, 3,3,5,5-tetramethyl-2,2-biphenol acts as a significant backbone in phosphorus-based ligand systems for calatysis. The oxidation of 2,4-dimethylphenol yields several different products including polycyclic compounds formed by C-H bond activation (Scheme 1). Therefore, designing a scalable process, in which the desired biphenol is selectively produced, is challenging.In the present work, we aim to develop MIPs that can be applied for selective electrosynthesis of the desired C-C coupled biphenol through electro-oxidation of the corresponding phenol. For this purpose, the functional monomer was selected based on the Gibbs free energy of its interaction with the target biphenol template in density functional theory (DFT) simulations. Complexation of the functional monomer with the template was confirmed by spectroscopic titrations. Electroactive monomers can polymerize to form either conducting or nonconducting polymers. In our system, a conductive MIP film was prepared using derivatized thiophene functional monomers. Then, the template extraction process was optimized. Electro-oxidation of 2,4-dimethyl phenol was studied in detail to reach as high yield as possible of the desired biphenol product at a bare platinum electrode. HPLC-MS was used to identify the substrate and products of the electrosynthesis. Then, selectivity of the electrosynthesis study was performed for the MIP film-coated electrode in comparison to a non-imprinted polymer (NIP) film-coated electrode, and a bare electrode. Figure 1