Beyond Frameworks: Structuring Reticular Materials across Nano‐, Meso‐, and Bulk Regimes

Abstract

Reticular materials are of high interest for diverse applications, ranging from catalysis and separation to gas storage and drug delivery. These open, extended frameworks can be tailored to the intended application through crystal‐structure design. Implementing these materials in application settings, however, requires structuring beyond their lattices, to interface the functionality at the molecular level effectively with the macroscopic world. To overcome this barrier, efforts in expressing structural control across molecular, nano‐, meso‐, and bulk regimes is the essential next step. In this Review, we give an overview of recent advances in using self‐assembly as well as externally controlled tools to manufacture reticular materials over all the length scales. We predict that major research advances in deploying these two approaches will facilitate the use of reticular materials in addressing major needs of society.

Emergent electrochemical functions and future opportunities of hierarchically constructed metal–organic frameworks and covalent organic frameworks

“…However, it is still challenging to design these types of 3D reticular materials with intrinsic conductive nature. 4,22 Although some state-of-the-art progress has been reported very recently, few research studies have attempted to control their hierarchical constructions of the conductive 3D MOFs and COFs. On the other hand, to use the unique features of 3D MOFs including a high accessible surface area and chemical tenability, some researchers reported composite materials of insulating MOFs in electrochemical applications.…”

“…Spatial and architectural design of materials from the molecular level to meso-/macroscopic scale has attracted material scientists. [1][2][3][4] To implement fundamental properties of materials in practical applications, it is highly important to design structural features in multiple length scales with optimal properties depending on the target applications. Referring to the past research, the concept of the spatial and architectural design of materials across the multiple length scales has been proven in the field of traditional porous inorganic materials, such as ceramics.…”

“…22 Recently, research studies on MOFs and COFs have gradually shifted to optimize the hierarchical construction of MOFs and COFs for their applications. 4,18,23 Besides, focusing on the reticular network, the multiple-pore skeletons 24 and multiple functional groups 25,26 also are recognized as hierarchical constructions.…”

Assembly and Covalent Cross-Linking of an Amine-Functionalised Metal-Organic Cage

“…The applications of metal-organic frameworks (MOFs) have been rapidly expanding, with recent studies utilizing MOFs as crystallization matrices ( Bloch et al, 2015 ), sacrificial scaffolds for hierarchical porosity ( Dang et al, 2017 ; Haase et al, 2020 ), and protective agents in biomedicine ( Yang and Yang, 2020 ; Liang et al, 2021 ). The attractive properties of MOFs have largely been underpinned by important design principles surrounding their net topology ( Robson 2000 ), isoreticular chemistry ( Furukawa et al, 2013 ), and post-synthetic chemistry ( Mandal et al, 2021 ).…”

Sol–gel based structural designs of macropores and material shapes of metal–organic framework gels

“…[5] In addition, by optimizing this reorganization process, the mesopores derived from the space between the primary particles can be controlled with target pore size. We believe the methodology of controlling macropores and material shapes of MOF gels, which have been generalized in this study, will be a platform to connect reticular chemistry and bulk materials [12] through further investigation of crystallization and/or functionalization conditions of MOF gels into the materials with controlled multimodal pore structures. In the future, we aim to develop a novel class of model porous materials which have well-defined hierarchical structures and reticular structures toward investigation for the further applications.…”