Incorporating a D–A–D-Type Benzothiadiazole Photosensitizer into MOFs for Photocatalytic Oxidation of Phenylsulfides and Benzylamines

Abstract

Oxidation and removal of highly toxic sulfides and amines are particularly important for environmental and human security but remain challenging. Here, incorporating an excellent photosensitizer, donor–acceptor–donor (D–A–D)-type 4,4′-(benzo­[c]­[1,2,5]­thiadiazole-4,7-diyl)­dibenzoic (H2L), into metal–organic frameworks (MOFs) has been manifested to promote the charge separation, affording four three-dimensional (3D) MOFs (isostructural 1-Co/1-Zn with Co2/Zn2 units, and 2-Gd/2-Tb with Gd/Tb-cluster chains) as photocatalysts in the visible light-driven air–O2-mediated catalytic oxidation and removal of hazardous phenylsulfides and benzylamines. Impressively, structure–property correlation illustrated that the transition metal centers assembled in MOFs play an important role in the photocatalytic activity, and we can conclude that 1-Zn can be a robust heterogeneous catalyst possessing good light adsorption and fast charge separation in oxidation removal reactions of both benzylamines and phenylsulfides under visible light irradiation and room temperature with excellent activity/selectivity, stability, and reusability.

Unravelling the photobehavior of a 2,1,3-benzothiadiazole-based HOF and its molecular units: experimental and theoretical insights into their spectroscopic properties in solution and in the solid state

“…35,36,41,42 Thus, these photoinduced properties make these systems very attractive materials to investigate for their possible applications in organic light-emitting diodes (OLEDs) 43–45 and organic photovoltaic cells 46,47 and for use in the construction of novel porous materials with enhanced luminescent properties. 48–53…”

Isoreticular Azobenzene Functionalization of Ultrastable Lead Chloride Hybrids for Enhanced Photocatalytic Aerobic Oxidation

“…Compared to the zigzag 3,3′-abdc, the straight, linear configuration of 4,4′-abdc afforded the expansion of porosity, resulting in 1D pore channels of increased size measuring 7.5 × 7.5 Å 2 in TMOF-6-4azo (Figure c and S2b). Notably, the π···π interactions of adjacent abdc ligands are present in both TMOF-6-3azo and TMOF-6-4azo (Figure S5), contributing not only to structural stability but also to facilitating efficient charge transfer for photocatalysis. , …”

“…Notably, the π•••π interactions of adjacent abdc ligands are present in both TMOF-6-3azo and TMOF-6-4azo (Figure S5), contributing not only to structural stability but also to facilitating efficient charge transfer for photocatalysis. 32,33 TMOF-6, TMOF-6-3azo, and TMOF-6-4azo were synthesized with high yield (74−78%) and high phase purity, based on the good matchings between the experimental powder Xray diffraction (PXRD) patterns and the simulated patterns from the single-crystal data (Figures S6−S8). The high chemical stability of both materials was performed by incubation in aqueous solutions over a wide range of pH (4−11) as well as organic solvents (e.g., MeOH and DCM) at room temperature.…”