Postsynthetic Modification of Metal-Organic Layers.

Abstract

ConspectusMetal-organic layers (MOLs), as a subclass of two-dimensional (2D) metal-organic frameworks (MOFs), have gained prominence in materials science by combining the structural versatility of MOFs with the unique physical and chemical properties of 2D materials. MOLs consist of metal oxide clusters connected by organic ligands, forming periodically extended 2D architectures with tunable properties and large surface areas. These characteristics endow MOLs with significant potential for applications in catalysis, sensing, energy storage, and biomedicine.The synthesis of MOLs predominantly follows two key pathways: top-down exfoliation of bulk layered MOFs and bottom-up assembly from molecular building units. The exfoliation method allows for the isolation of ultrathin MOL sheets from bulk precursors, but scalability and structural defects present ongoing challenges. In contrast, the bottom-up assembly offers more precise control over structural design, enabling the formation of MOLs with tailored chemical functionalities and morphologies. By carefully selecting linkers and synthetic conditions, researchers have successfully constructed MOLs with diverse geometric configurations including linear, triangular, and rectangular ligand motifs. Nevertheless, achieving consistent monolayer formation and controlling lateral dimensions remain critical challenges for the widespread application of these materials.A defining advantage of MOLs is their exceptional amenability to postsynthetic modification (PSM). PSM strategies enable fine-tuning of MOL properties and the introduction of novel functionalities without compromising the integrity of the underlying framework. Four principal approaches to PSM have been established: (1) linker modification, where additional coordination sites facilitate selective metalation or functional group incorporation; (2) secondary building unit (SBU) modification, using replaceable sites perpendicular to the MOL plane for targeted functionalization; (3) dual modification, integrating linker and SBU functionalization to achieve complex multifunctional platforms; and (4) multilevel assembly, incorporating MOLs into larger hierarchical architectures such as biomimetic systems and composite materials.These versatile modification strategies have unlocked novel applications of MOLs, including single-site catalysis, photocatalysis, and artificial photosynthetic systems. For instance, MOLs functionalized with transition metal complexes have more accessible reactive sites than conventional MOFs for faster substrate transport. Additionally, MOLs interfaced with biomimetic systems, such as liposomes and proteins, have demonstrated significant promise in photochemical energy conversion and selective oxidation processes.Despite these advancements, several key obstacles persist. Achieving uniform monolayer thickness while preventing multilayer aggregation remains a formidable task, necessitating deeper insights into the thermodynamic and kinetic factors governing MOL growth. Furthermore, the behavior of MOLs during drying, adsorption, and structural modification often deviates from classical models, suggesting the involvement of complex interfacial phenomena that warrant further investigation. Addressing these challenges will be crucial for harnessing the full potential of MOLs in next-generation functional materials.In summary, MOLs represent a versatile and dynamic class of materials that offer opportunities for innovation across diverse scientific disciplines. By advancing synthetic methodologies and deepening our understanding of postsynthetic modification strategies, researchers can continue to expand the functional landscape of MOLs, paving the way for transformative applications in catalysis, energy conversion, and beyond.