破译功能协同作用在催化分子组装器中的作用：通过逆合成接头剪切增强催化作用的概念证明,Materials Chemistry Frontiers

当前位置： X-MOL 学术 › Mater. Chem. Front. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

破译功能协同作用在催化分子组装器中的作用：通过逆合成接头剪切增强催化作用的概念证明
Materials Chemistry Frontiers ( IF 6.0 ) Pub Date : 2023-01-13 , DOI: 10.1039/d2qm01177h
Ranadip Goswami _{1,

2,

3} , Arun Karmakar _{1,

4} , Sonal Rajput ₂ , Manpreet Singh _{1,

2} , Subrata Kundu _{1,

4} , Subhadip Neogi _{1,

2}

Affiliation

人工催化机械能够在金属有机框架 (MOF) 中即兴进行目的驱动的孔功能工程，以追求可再生能源和仿生氢键供体 (HBD) 有机催化。尽管具有挑战性，但通过自下而上的 Lego® 化学在此类材料中进行系统的功能标记是非常受欢迎的，并且必须采用连贯的自组装设计原则来解决这些令人担忧的问题。我们展示了一种独特的接头剪式策略，以开发具有来自电活性和氢键操作支柱的氧化还原活性 Co( II ) 节点的超稳健 MOF ，这体现了前所未有的双峰可持续催化联盟在一个单一的、多方面的平台上进行串联功能安装。该框架在碱性介质中表现出高效和持久的析氧反应 (OER)，具有显着的电催化参数，跻身于最著名的 MOF 之列，甚至优于一些基准催化剂。这种微孔容器通过温和条件的 HBD 反应进一步描述了最稀有的 –NH ₂ -hook 介导的可回收 Friedel–Crafts 烷基化和 β-硝基苯乙烯，并表现出分子尺寸介导的尺寸选择性。电化学动态接头中的轻松电荷转移和悬垂配体中有利的两点 H 键的协同作用支持了单独的催化效率，如下所述分析物诱导的伴随荧光修饰和变量控制实验。重要的是，任务特定位点在 OER 和 HBD 催化中的关键作用通过逆合成片段化 MOF 的协同功能组装并置三个同构 Co( II ) MOF的性能得到验证。这种功能主链顺序修剪的新策略全面展示了本系统的优越性，并导致设计出一种独特的催化组装器，作为未来分子机器的蓝图，以改进催化方向。

"点击查看英文标题和摘要"

Deciphering the role of functional synergy in a catalytic molecular assembler: a proof of concept for boosted catalysis via retrosynthetic linker scissoring

Artificial catalytic machinery enables improvising purpose-driven pore functionality engineering in metal–organic frameworks (MOFs) in pursuit of renewable energy sources and biomimetic hydrogen-bond-donating (HBD) organo-catalysis. Though challenging, systematic functional-tagging via bottom-up Lego® chemistry in such materials is highly sought and obligates a coherent design principle of self-assembly to resolve these alarming issues. We demonstrate a unique linker scissoring strategy to develop an ultra-robust MOF with redox-active Co(II) nodes from electroactive and H-bond operative struts, which exemplifies the unprecedented alliance of bimodal sustainable catalysis via tandem functionality installation over a single, multifaceted platform. The framework displays highly efficient and durable oxygen evolution reactions (OERs) in alkaline media with notable electrocatalytic parameters that rank among the best-known MOFs and even outperforms some benchmark catalysts. This microporous vessel further delineates the rarest –NH₂-hook-mediated recyclable Friedel–Crafts alkylation of indole and β-nitrostyrene via mild-condition HBD reactions and exhibits molecular-dimension-mediated size selectivity. The synergistic involvement of facile charge transfer in electrochemically dynamic linkers and favourable two-point H-bonding in pendent ligands underpins individual catalytic efficiency as elaborated via analyte-induced concomitant fluorescence modification and variable control experiments. Significantly, the key roles of task-specific sites in both OERs and HBD catalysis are validated from juxtaposing the performance of three isostructural Co(II) MOFs via the cooperative functional assembly of retrosynthetically fragmented MOFs. This novel strategy of sequential trimming of the functional backbone comprehensively demonstrates the superiority of the present system and leads to devising a unique catassembler as a blueprint of futuristic molecular machines for improved catalytic direction.

更新日期：2023-01-13

点击分享查看原文

点击收藏

阅读更多本刊新发论文