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.

Post‐Nickelation of a Crystalline Trinuclear Copper Organic Framework for Synergistic Photocatalytic Carbon Dioxide Conversion

“…Successful complexation of nickel ion with USTB‐12 is also verified by the presence of Ni signal in the XPS spectrum of USTB‐12(Ni). The Cu 2p XPS spectrum of USTB‐11(Cu) with trinuclear copper moiety displays two kinds of binding energies at 932.5 and 934.3 eV (Figure S18) due to the Cu(2p 3/2 ) orbitals of Cu I and Cu II ions, [9c] respectively, revealing the mixed Cu I /Cu II state nature of Cu element in this material. This is also true for USTB‐11(Cu,Ni) (Figure S18).…”

A CuI Cluster‐Based Covalent Metal‐Organic Framework as a Photocatalyst for Efficient Visible‐Light‐Driven Reduction of CO2

“…In the high‐resolution XPS spectrum of Cu 3 L 3 , the Cu 2p 3/2 binding energies at 932.6 and 934.6 eV were assigned to Cu I and Cu II , respectively (Figure 1d). [18,21] Cu II was derived from the oxidation of Cu I on the surface of Cu clusters, and the change of Cu valence had no impact on the cyclic triangular skeleton of Cu clusters [22] . Notably, the Cu 2p 3/2 binding energy of JNM‐2 displayed a slight shift of 0.5 eV in comparison with Cu 3 L 3 , which was probably attributed to the fact that the Cu clusters and the organic ligands were successfully linked by covalent bonds and an internal electric field was formed between them, thus facilitating the intramolecular electron transfer [8] .…”

Soft Metal Cations Trigger Sandwich‐Cluster Luminescence of a New Au(I)‐Vinylimidazolate Cyclic Trinuclear Complex

“…[6][7][8][9][10][11][12][13][14][15][16][17] Beyond that, ordered materials constructed from CTCs are being pursued in very recent years for their controllable skeletons and excellent optical/catalytic performances. [18][19][20][21][22][23][24][25] The clusters herein are formed by sandwiching a foreign closed-shell metal cation between two gold(I) CTC molecules, resulting in an [Au 3 ]…M + …[Au 3 ] chemical formula for the resulting heptanuclear cluster. [6,[26][27][28][29][30][31][32] Since they were discovered in 1998, [28] few reports on structure determinations and luminescence properties only cover the central metal cations of Ag + and Tl + .…”