具有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。
Bifunctional Metal-Organic Layer with Organic Dyes and Iron Centers for Synergistic Photoredox Catalysis.
机构信息
Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States.
College of Chemistry and Chemical Engineering, iCHEM, State Key Laboratory of Physical Chemistry of Solid Surface, Xiamen University, Xiamen 361005, PR China.
出版信息
J Am Chem Soc. 2021 Mar 3;143(8):3075-3080. doi: 10.1021/jacs.1c01083. Epub 2021 Feb 19.
Here we report the design of a bifunctional metal-organic layer (MOL), , by bridging eosin Y (EY)-capped Hf 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) as the catalytic center, efficiently catalyzes aminotrifluoromethylation, hydroxytrifluoromethylation, and chlorotrifluoromethylation of alkenes. also catalyzes the synthesis of CF-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 enhance catalytic activity while inhibiting their mutual deactivation, leading to high turnover numbers of up to 1840 and good recyclability of the MOL catalyst.
在这里，我们报告了一种双功能金属-有机层（MOL）的设计，该 MOL 通过桥联曙红 Y（EY）封端的 Hf 次级构筑单元（SBUs）与 Fe-TPY（TPY=4'-(4-羧基苯基)[2,2':6',2''-三联吡啶]-5,5''-二羧酸酯）配体来实现。由于有机染料 EY 是一种有效的光敏剂，而 TPY-Fe(OTf)是催化中心，因此 可以高效地催化烯烃的氨三氟甲基化、羟三氟甲基化和氯三氟甲基化反应。它还可以催化多达 2.2nm 大小的大生物活性分子如鱼藤酮、雌酮和阿达帕林的 CF 取代衍生物的合成。EY 和铁中心之间的接近以及它们在 MOL 催化剂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，从而使 MOL 催化剂的周转数高达 1840，并且具有良好的可回收性。
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