Precise Distance Control and Functionality Adjustment of Frustrated Lewis Pairs in Metal–Organic Frameworks

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Journal of the American Chemical Society Pub Date : 2024-04-17 DOI:10.1021/jacs.4c03133
Wenhao Chen, Shenhui Li*, Lezhi Yi, Ziyi Chen, Zihao Li, Yifan Wu, Wei Yan, Feng Deng* and Hexiang Deng*, 
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Abstract

We report the construction of frustrated Lewis pairs (FLPs) in a metal–organic framework (MOF), where both Lewis acid (LA) and Lewis base (LB) are fixed to the backbone. The anchoring of a tritopic organoboron linker as LA and a monotopic linker as LB to separate metal oxide clusters in a tetrahedron geometry allows for the precise control of distance between them. As the type of monotopic LB linker varies, pyridine, phenol, aniline, and benzyl alcohol, a series of 11 FLPs were constructed to give fixed distances of 7.1, 5.5, 5.4, and 4.8 Å, respectively, revealed by 11B–1H solid-state nuclear magnetic resonance spectroscopy. Keeping LA and LB apart by a fixed distance makes it possible to investigate the electrostatic effect by changing the functional groups in the monotopic LB linker, while the LA counterpart remains unaffected. This approach offers new chemical environments of the active site for FLP-induced catalysis.

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金属有机框架中受挫路易斯对的精确距离控制和功能调整
我们报告了在金属有机框架(MOF)中构建受挫路易斯对(FLPs)的情况,其中路易斯酸(LA)和路易斯碱(LB)都固定在骨架上。将三位有机硼连接体(LA)和单位连接体(LB)分别锚定在四面体几何形状的独立金属氧化物簇上,可以精确控制它们之间的距离。11B-1H 固态核磁共振波谱显示,由于单位 LB 连接物的类型不同(吡啶、苯酚、苯胺和苯甲醇),构建的 11 个 FLP 系列的固定距离分别为 7.1、5.5、5.4 和 4.8 Å。将 LA 和 LB 保持固定的距离,可以通过改变 LB 单配位连接体中的官能团来研究静电效应,而 LA 对应的连接体则不受影响。这种方法为 FLP 诱导催化的活性位点提供了新的化学环境。
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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