skip to main content

SciTech ConnectSciTech Connect

Title: Porphyrin-Metalation-Mediated Tuning of Photoredox Catalytic Properties in Metal–Organic Frameworks

Photoredox catalytic activation of organic molecules via single-electron transfer processes has proven to be a mild and efficient synthetic methodology. However, the heavy reliance on expensive ruthenium and iridium complexes limits their applications for scale-up synthesis. To this end, photoactive metal–organic frameworks (MOFs) exhibit unique advantages as novel heterogeneous photocatalytic systems, yet their utilization toward organic transformations has been limited. Here we describe the preparation and synthetic applications of four isostructural porphyrinic MOFs, namely, UNLPF-10a, -10b, -11, and -12, which are composed of free base, InIII-, SnIVCl2-, and SnIV-porphyrin building blocks, respectively. We demonstrate that the metalation with high valent metal cations (InIII and SnIV) significantly modifies the electronic structure of porphyrin macrocycle and provides a highly oxidative photoexcited state that can undergo efficient reductive quenching processes to facilitate organic reactions. In particular, UNLPF-12 exhibits both outstanding photostability and efficient photocatalytic activities toward a range of important organic transformations including aerobic hydroxylation of arylboronic acids, amine coupling, and the Mannich reaction.
Authors:
; ; ; ; ; ; ;
Publication Date:
OSTI Identifier:
1247342
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Catalysis; Journal Volume: 5; Journal Issue: 9
Publisher:
American Chemical Society
Research Org:
Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US)
Sponsoring Org:
UNIVERSITYOTHER
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY