An Imine‐Linked Metal–Organic Framework as a Reactive Oxygen Species Generator

Abstract

A new metal–organic framework (MOF) with both coordination linkages and covalent linkages is prepared by coordinating CuI with pyrazolate for an aldehyde‐functionalized trinuclear complex, and subsequent imine condensation with p‐phenylenediamine, a reaction typical for covalent organic framework (COF) synthesis. This MOF×COF collaboration yields FDM‐71 with honeycomb layers stacked in eclipsed fashion. After dissociating the CuI‐pyrazolate coordination in FDM‐71, the obtained organic components carry the information of structural defects, and thus vacancy identity (aldehyde‐based unit vacancy and amine‐based unit vacancy) and concentration are definitely resolved. Further to the redox catalytic activity inherited from the complex, FDM‐71 features effective photosensitizing activity. The two functions integrated in one well‐defined structure is demonstrated by its high efficiency in decomposing H2O2 and consequent excitation of O2 to reactive oxygen species.

Facile synthesis of C3N4-supported metal catalysts for efficient CO2 photoreduction

“…In this context, tremendous efforts have been devoted to the preparation of atomically dispersed metal photocatalysts. Metal-organic frameworks (MOFs), a class of crystalline porous materials where metal atoms are separated in atomic level, have been demonstrated to be one of the most promising candidates for fabrication of highly dispersed metal catalysts [19][20][21][22][23][24][25][26][27][28]. MOFderived metal catalysts usually inherit the high surface area and porosity of MOFs, which facilitate the mass transportation and charge transfer in catalytic processes, and thus often show enhanced catalytic activity [29][30][31].…”

Mixed‐Metal MOF‐Derived Hollow Porous Nanocomposite for Trimodality Imaging Guided Reactive Oxygen Species‐Augmented Synergistic Therapy

“…Specifically, the deconvoluted peak at 932.9 eV refers to Cu + 2p 3/2 , while the peak at 934.4 eV is for Cu 2+ 2p 3/2 ; the peak at 942.0 eV indicates the Cu 2+ satellite (Figure 2f). [ 23,24 ] The relative atomic percentage of Cu + and Cu 2+ was 34.1% and 65.9% from integrating the deconvoluted peak areas (Figure 2g). [ 23 ] After H 2 O 2 treatment, the proportion of Cu + decreased to 13.9%.…”

“…[ 23,24 ] The relative atomic percentage of Cu + and Cu 2+ was 34.1% and 65.9% from integrating the deconvoluted peak areas (Figure 2g). [ 23 ] After H 2 O 2 treatment, the proportion of Cu + decreased to 13.9%. Thus, Cu + ions were efficiently integrated and could be used to mediate Fenton‐like reaction in the presence of H 2 O 2 .…”

Vacancies in Metal−Organic Frameworks: Formation, Arrangement, and Functions

“…For MOF vacancies by structural modulators or fragmented linker strategy, NMR spectroscopy after MOF digestion is a powerful tool to determine the ratio between the linkers and modulators/fragments, and thus amount of the defects can be concluded. [195][196][197][198] However, the analysis could only track the organic components in the MOFs, and thus the information on cluster vacancies is not available. When NMR is combined with TGA and EA, an accurate structural formula showing defects with missing organic components (missing linker or missing functionality) and/or missing inorganic components (missing cluster or missing metal) could be obtained.…”