Postsynthetic Modification: An Enabling Technology for the Advancement of Metal–Organic Frameworks

Abstract

Metal–organic frameworks (MOFs) are a class of porous materials with immense chemical tunability derived from their organic and inorganic building blocks. Presynthetic approaches have been used to construct tailor-made MOFs, but with a rather restricted functional group scope limited by the typical MOF solvothermal synthesis conditions. Postsynthetic modification (PSM) of MOFs has matured into an alternative strategy to broaden the functional group scope of MOFs. PSM has many incarnations, but two main avenues include (1) covalent PSM, in which the organic linkers of the MOF are modified with a reagent resulting in new functional groups, and (2) coordinative PSM, where organic molecules containing metal ligating groups are introduced onto the inorganic secondary building units (SBUs) of the MOF. These methods have evolved from simple efforts to modifying MOFs to demonstrate proof-of-concept, to becoming key synthetic tools for advancing MOFs for a range of emerging applications, including selective gas sorption, catalysis, and drug delivery. Moreover, both covalent and coordinative PSM have been used to create hierarchal MOFs, MOF-based porous liquids, and other unusual MOF materials. This Outlook highlights recent reports that have extended the scope of PSM in MOFs, some seminal reports that have contributed to the advancement of PSM in MOFs, and our view on future directions of the field.

In Situ Porphyrin Substitution in a Zr(IV)‐MOF for Stability Enhancement and Photocatalytic CO2 Reduction

“…The 13 CO 2 isotope-labeling experiments were also conducted. In the mass spectrum, the peak at m/z = 29 can be attributed to 13 CO (Figure S17, Supporting Information), further confirming that the product originates from CO 2 reduction, rather than from impurities or any other carbon sources. These results definitely illustrate the role of active metalloporphyrin sites which are immobilized in the BUT-110 framework for catalyzing the photoinduced CO 2 reduction.…”

“…[1][2][3][4][5][6][7][8][9][10] In virtue of many well-developed construction strategies, hundreds of thousands of MOFs are obtained through direct or post-synthetic approaches, contributing enormous structural and functional diversity. [11][12][13][14] Despite a few robust MOFs, such as the famous UiO, [15,16] ZIF, [17,18] MOF, [19][20][21][22] MIL, [23,24] PCN, [25][26][27] and NU series, [28,29] most of existing MOFs are far away from practical use due to their relatively weak stability. Therefore, developing methods to stabilize labile MOFs would help remove the limitation on their application scope imposed by the framework fragility, and thus unlock more possibilities for the MOF community.…”

Zn‐MOF Encapsulated Antibacterial and Degradable Microneedles Array for Promoting Wound Healing

“…These drawbacks have seriously restricted the development of MNs in the field of promoting wound healing. [12][13][14][15][16][17] Thus, new-type MNs arrays with diverse compositions and expected functions are still anticipated in clinical practice. [18][19][20][21][22] In this paper, we propose a novel Zn-MOF encapsulated MNs array with features of anti-bacterial activity and degradability for promoting wound healing, as schemed in Figure 1.…”

Cobalt metal–organic framework-based ZIF-67 for the trace determination of herbicide molinate by ion mobility spectrometry: investigation of different morphologies

“…Consequently, the IMS technique could be used for recognizing different blends, including toxic compounds (herbicides, pesticides, and insecticides), warfare agents, and abuse and clinical drugs. 7 Metal-organic frameworks (MOFs), a class of porous materials, are essential for numerous scientic studies, [8][9][10] such as catalysts, gas absorption, drug delivery, separation, electronic devices, and sensors due to their essential features, including large surface area, tunable organic ligands, high crystallization, large pore volume, and adjustable pore size. [11][12][13] Zeolitic imidazolate frameworks (ZIFs), as a specic and new category of metal-organic frameworks, consist of metal ions and imidazolate linking agents having intrinsic porosity as well as extraordinary chemical and thermal stability.…”