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含曙红Y的金属有机框架作为惰性C-H键直接光活化的多相催化剂。

Eosin Y-Containing Metal-Organic Framework as a Heterogeneous Catalyst for Direct Photoactivation of Inert C-H Bonds.

作者信息

Zhao Liang, Du Zenggang, Ji Guanfeng, Wang Yefei, Cai Wei, He Cheng, Duan Chunying

机构信息

State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, P. R. China.

出版信息

Inorg Chem. 2022 May 16;61(19):7256-7265. doi: 10.1021/acs.inorgchem.1c03813. Epub 2022 May 4.

Abstract

Xanthene dyes as a class of ideal organic homogeneous photocatalyst have received significant attention in C-H bond activation; however, the inherent nature of fast carrier recombination/deactivation and low stability limits their practical applications. Herein, by the ingenious decoration of eosin Y into a porous metal-organic framework (MOF), a high-performance heterogeneous MOF-based photocatalyst was prepared to efficiently activate inert C-H bonds on the reactants via the hydrogen atom transfer pathway for the functionalization of the C-H bonds. Taking advantage of the fixation effect of a rigid framework, the incorporation of eosin Y into MOF leads to great enhancement of their chemical durability. More importantly, by the introduction of the second auxiliary ligand, the carbonyl groups of xanthene on the eosin Y dyes were perfectly retained and periodically aligned within the confined channels of this rigid framework, which could effectively form excited state radicals to prompt inert C-H bond activation, promoting reaction efficiency by the host-guest supramolecular interaction. New eosin Y-based MOFs were recyclable for six times without reducing photocatalytic activity. This eosin Y functionalized MOF-based heterogeneous photocatalytic system provides an availably catalytic avenue to develop a scalable and sustainable synthetic strategy for the practical application of organic dyes.

摘要

作为一类理想的有机均相光催化剂,呫吨染料在C-H键活化方面受到了广泛关注;然而,快速的载流子复合/失活以及低稳定性的固有特性限制了它们的实际应用。在此,通过将曙红Y巧妙地修饰到多孔金属有机框架(MOF)中,制备了一种高性能的基于MOF的非均相光催化剂,通过氢原子转移途径有效活化反应物上的惰性C-H键,实现C-H键的官能化。利用刚性框架的固定作用,将曙红Y引入MOF可大大提高其化学耐久性。更重要的是,通过引入第二种辅助配体,曙红Y染料上呫吨的羰基得以完美保留,并在该刚性框架的受限通道内周期性排列,这可以有效地形成激发态自由基以促进惰性C-H键的活化,通过主客体超分子相互作用提高反应效率。新型的基于曙红Y的MOF可循环使用六次而不降低光催化活性。这种基于曙红Y功能化MOF的非均相光催化体系为开发一种可扩展且可持续的合成策略以实现有机染料的实际应用提供了一条有效的催化途径。

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