美国芝加哥大学Wenbin Lin课题组宣布他们研究出含有机染料和铁中心的双功能金属有机层用于协同光氧化还原催化。 2021年2月19日出版的《美国化学会杂志》发表了这项成果。

本文报道了一种双功能金属有机层(MOL) Hf-EY-Fe的设计，该层是通过用Fe-TPY (TPY = 4 '' -(4-羧基苯基)[2,2':6',2" -三联吡啶]-5,5 "-二羧酸)配体桥接eosin Y (EY)-封端Hf6 二级构造单元(SBUs)来实现的。以有机染料EY为高效光敏剂，TPY-Fe(OTf)2为催化中心，Hf-EY-Fe高效催化烯烃的氨基三氟甲基化、羟基三氟甲基化和氯三氟甲基化。

Hf-EY-Fe还催化合成最大生物活性分子（如鱼藤酮，雌酮和阿达帕林）的CF₃取代衍生物，尺寸最大为2.2 nm。EY与铁中心之间的距离以及它们在Hf-EY-Fe中的位点隔离增强了催化活性，同时抑制了它们的相互失活，从而导致高达1840的高周转率和MOL催化剂的良好可回收性。

附：英文原文

Title: Bifunctional Metal–Organic Layer with Organic Dyes and Iron Centers for Synergistic Photoredox Catalysis

Author: Yangjian Quan, Wenjie Shi, Yang Song, Xiaomin Jiang, Cheng Wang, Wenbin Lin

Issue&Volume: February 19, 2021

Abstract: Here we report the design of a bifunctional metal–organic layer (MOL), Hf-EY-Fe, by bridging eosin Y (EY)-capped Hf6 secondary building units (SBUs) with Fe-TPY (TPY = 4′-(4-carboxyphenyl)[2,2′:6′,2′′-terpyridine]-5,5′′-dicarboxylate) ligands. With the organic dye EY as an efficient photosensitizer and TPY-Fe(OTf)2 as the catalytic center, Hf-EY-Fe efficiently catalyzes aminotrifluoromethylation, hydroxytrifluoromethylation, and chlorotrifluoromethylation of alkenes. Hf-EY-Fe also catalyzes the synthesis of CF3-substituted derivatives of large bioactive molecules such as rotenone, estrone, and adapalene with sizes of up to 2.2 nm. The proximity between EY and iron centers and their site isolation in Hf-EY-Fe enhance catalytic activity while inhibiting their mutual deactivation, leading to high turnover numbers of up to 1840 and good recyclability of the MOL catalyst.

DOI: 10.1021/jacs.1c01083

Source: https://pubs.acs.org/doi/10.1021/jacs.1c01083