期刊
ACS CATALYSIS
卷 5, 期 9, 页码 5283-5291出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.5b00941
关键词
metal-organic frameworks; photocatalysis; microporous materials; porphyrins; metalation
资金
- University of Nebraska-Lincoln
- American Chemical Society Petroleum Research Fund [53678-DNI10]
- National Science Foundation through Nebraska MRSEC [DMR-1420645]
- Divisions of Chemistry (CHE) and Materials Research (DMR), National Science Foundation [NSF/CHE-1346572]
- U.S. DOE [DE-AC02-06CH11357]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1346572] Funding Source: National Science Foundation
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, In-III-, (SnCl2)-Cl-IV-, and Sn-IV-porphyrin building blocks, respectively. We demonstrate that the metalation with high valent metal cations (In-III and Sn-IV) 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.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据