The Effect of Linker‐to‐Metal Energy Transfer on the Photooxidation Performance of an Isostructural Series of Pyrene‐Based Rare‐Earth Metal–Organic Frameworks

Abstract

The tetratopic linker, 1,3,6,8‐tetrakis(p‐benzoic acid)pyrene (H4TBAPy) along with rare‐earth (RE) ions is used for the synthesis of 9 isostructures of a metal–organic framework (MOF) with shp topology, named RE‐CU‐10 (RE = Y(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Lu(III)). The synthesis of each RE‐CU‐10 analogue requires different reaction conditions to achieve phase pure products. Single crystal X‐ray diffraction indicates the presence of a RE9‐cluster in Y‐ to Tm‐CU‐10, while a RE11‐cluster is observed for Yb‐ and Lu‐CU‐10. The photooxidation performance of RE‐CU‐10 analogues is evaluated, observing competition between linker‐to‐metal energy transfer versus the generation of singlet oxygen. The singlet oxygen produced is used to detoxify a mustard gas simulant 2‐chloroethylethyl sulfide, with half‐lives ranging from 4.0 to 5.8 min, some of the fastest reported to date using UV‐irradiation and < 1 mol% catalyst, in methanol under O2 saturation.

Smart Stimulation Response of a Pyrene-Based Lanthanide(III) MOF: Fluorescence Enhancement to HX (F and Cl) or R-COOH and Artificial Applicable Film on HCl Vapor Sensing

“…The crystallographic data, selected bond lengths, and bond angles of complex 1 are given in Tables S1–S3. Although Ln-MOF based on H 4 TBAPy had been reported, the coordination environment of metal-centered Pr­(III) ions of this work was completely different from that reported for Ln-MOF based on H 4 TBAPy in the literature. − …”

Ho(III)-Based Metal–Organic Framework for Water Pollution Treatment: Insights into Sensitive Phosphate Removal and Sensing in Aqueous Solution

“…This performance can be related to two phenomena: the energy transfers from the bpdc ligand to Ho 3+ sites, or the energy is transferred to other interactions. Furthermore, the absence of additional peaks in the solid-stated emission spectra of Ho-bpdc rules out the possibility of ligand–metal energy transfers . However, the quenching behavior can be interpreted as the energy released through nonradiative pathways …”

Fluoro-bridged rare-earth metal–organic frameworks

“…5) in MOFs. 57,70,71 A series of RE metals (RE = Y( iii ), Gd( iii ), Tb( iii ), Dy( iii ), Ho( iii ), Er( iii ), Tm( iii ), Yb( iii ), and Lu( iii )) with TBAPy resulted in shp -topology MOFs (RE-CU-10). An unusual RE 11 cluster (not shown) was found in the case of Yb( iii ) and Lu( iii ) with 2 metal ions caping the nonaclusters axially.…”