Edward Ailsa K, Ettlinger Romy, Janczuk Zuzanna Z, Hua Guoxiong, Morris Russell E, Kay Euan R
EaStCHEM School of Chemistry, University of St Andrews, St Andrews KY16 9ST, U.K.
TUM School of Natural Sciences, Technical University of Munich, Lichtenbergstr. 4, Garching b. München 85748, Germany.
J Am Chem Soc. 2025 Feb 12;147(6):5114-5124. doi: 10.1021/jacs.4c15261. Epub 2025 Jan 30.
Nanoparticles of highly porous metal-organic frameworks (MOFs) are some of the most exciting nanomaterials under development, with potential applications that range from biomedicine and catalysis to adsorption technologies. However, our synthetic methodologies to functionalize and manipulate MOF nanoparticles (NPs) are less well developed than they might be. Here we create MOF NPs derivatized with hydrazone units on their exterior, enabling chemospecific reversible dynamic covalent modification of structures on the external surface. Pairwise combinations of nanometer-sized building blocks with complementary dynamic covalent surface units can be used to prepare heterostructure assemblies (i.e., two MOFs with different structures and morphologies) and heteromaterial assemblies (a MOF with a nanoparticle of another kind, in this case gold) in which the directional molecular-level dynamic covalent links demand intimate mixing of the two nanoscale components. Crucially, the defining characteristic of the MOF components─their porosity─is minimally affected by the external functionalization and interparticle linking. The development of atomically precise dynamic covalent functionalization on the external surface of MOF NPs opens up new avenues for programmable frameworks with responsive behaviors and modular assembly of porous materials with precise control over the spatial organization of multiple nanoscale building blocks.
高度多孔的金属有机框架（MOF）纳米颗粒是目前正在开发的一些最令人兴奋的纳米材料，其潜在应用范围从生物医学、催化到吸附技术。然而，我们用于功能化和操控MOF纳米颗粒（NP）的合成方法的发展程度不如预期。在此，我们制备了在其外部衍生有腙单元的MOF NP，从而实现对外表面结构的化学特异性可逆动态共价修饰。具有互补动态共价表面单元的纳米级构建块的成对组合可用于制备异质结构组装体（即两种具有不同结构和形态的MOF）和异质材料组装体（一种MOF与另一种纳米颗粒，在此为金），其中定向的分子水平动态共价连接要求两种纳米级组分紧密混合。至关重要的是，MOF组分的决定性特征——其孔隙率——受外部功能化和颗粒间连接的影响最小。MOF NP外表面原子精确的动态共价功能化的发展为具有响应行为的可编程框架以及对多个纳米级构建块的空间组织进行精确控制的多孔材料模块化组装开辟了新途径。
