Harnessing a Pd4 Water-Soluble Molecular Capsule as a Size-Selective Catalyst for Targeted Oxidation of Alkyl Aromatics

Abstract

Molecular hosts with functional cavities can emulate enzymatic behavior through selective encapsulation of substrates, resulting in high chemo-, regio-, and stereoselective product formation. It is still challenging to synthesize enzyme-mimicking hosts that exhibit a narrow substrate scope that relies upon the recognition of substrates based on the molecular size. Herein, we introduce a Pd₄ self-assembled water-soluble molecular capsule [M₄L₂] (MC) that was formed through the self-assembly of a ligand L (4′,4‴′-(1,4-phenylene)bis(1′,4′-dihydro-[4,2′:6′,4″-terpyridine]-3′,5′-dicarbonitrile)) with the acceptor cis-[(en)Pd(NO₃)₂] [en = ethane-1,2-diamine] (M). The molecular capsule MC showed size-selective recognition towards xylene isomers. The redox property of MC was explored for efficient and selective oxidation of one of the alkyl groups of m-xylene and p-xylene to their corresponding toluic acids using molecular O₂ as an oxidant upon photoirradiation. Employing host–guest chemistry, we demonstrate the homogeneous catalysis of alkyl aromatics to the corresponding monocarboxylic acids in water under mild conditions. Despite homogeneous catalysis, the products were separated from the reaction mixtures by simple filtration/extraction, and the catalyst was reused. The larger analogues of the alkyl aromatics failed to bind within the MC’s hydrophobic cavity, resulting in a lower/negligible reaction outcome. The present study represents a facile approach for selective photo-oxidation of xylene isomers to their corresponding toluic acids in an aqueous medium under mild conditions.