De Novo Synthesis of Acridone-Based Zn-Metal-Organic Framework (Zn-MOF) as a Photocatalyst: Application for Visible Light-Mediated Oxidation of Sulfides and Enaminones.

Abstract

Acridone, a cyclic analogue of benzophenone that undergoes efficient intersystem crossing (ISC) to the triplet-excited state with near-unity quantum yield, was elaborated as a 3-connecting triacid linker, i.e., H3AcTA, to develop a photocatalytic metal-organic framework (MOF) for energy transfer applications; the triacid linker inherently features concave shapes, an attribute that is important for the construction of MOFs with significant porosity. Metal ion (Zn2+)-assisted self-assembly of the triacid yielded a Zn-MOF, i.e., Zn-AcTA, with a solvent-accessible volume of ca. 31%. The protection of the acridone chromophore in the MOF in conjunction with a wider cross-section of its absorption in the visible region renders the MOF an excellent heterogeneous photosensitizer for singlet oxygen (1O2) generation by energy transfer to the ground-state triplet oxygen (3O2). It is shown that the Zn-MOF can be applied as a photosensitizing catalyst for visible light-mediated oxidation of various sulfides to sulfoxides and enaminones to amino-esters via 1,2-acyl migration. It is further demonstrated that the photocatalyst can be easily recycled without any loss of catalytic activity and structural integrity. Based on mechanistic investigations, 1O2 is established as the reactive oxygen species in photocatalytic oxidation reactions. The results constitute the first demonstration of rational development of a photocatalytic MOF based on acridone for heterogeneous oxidations mediated by 1O2.