Reversible redox switching of magnetic order and electrical conductivity in a 2D manganese benzoquinoid framework

Liu, Lujia; DeGayner, Jordan A.; Sun, Lei; Zee, David Z.; Harris, T. David

doi:10.1039/c9sc00606k

Cited by 75 publications

(91 citation statements)

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“…Due to their large pores and vast synthetic tunability, metalorganic frameworks represent a promising template for the synthesis of anionic materials with structurally dened, weakly coordinated cations. [13][14][15] Thus far, crystallographic location of these charge-balancing cations has been limited to various bulky alkylammonium ions [16][17][18][19][20] and cobaltocenium, 21 with only a few examples of monoatomic cations being structurally characterized. [22][23][24][25] Interestingly, certain framework materials containing small, charge-dense monoatomic cations have been found to exhibit enhanced gas uptake and binding relative to their parent materials, 20,[22][23][24][25][26][27] but these interactions are much weaker than those characterized in zeolites containing the same cations.…”

Section: Introductionmentioning

confidence: 99%

Crystallographic characterization of the metal–organic framework Fe₂(bdp)₃ upon reductive cation insertion

2020

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Section: Introductionmentioning

confidence: 99%

Crystallographic characterization of the metal–organic framework Fe₂(bdp)₃ upon reductive cation insertion

2020

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“…A unique application is the electric field induced switching of gas permeation in a MOF membrane 45 . Switchable magnetic and electronic properties are also emerging for, in particular, information processing technologies 12,46,47 . One visionary application is a switchable catalyst, a catalytically active MOF exposing its active sites during opening of the porous system 48 .…”

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confidence: 99%

Four-dimensional metal-organic frameworks

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Recognising timescale as an adjustable dimension in porous solids provides a new perspective to develop novel four-dimensional framework materials. The deliberate design of three-dimensional porous framework architectures is a developed field; however, the understanding of dynamics in open frameworks leaves a number of key questions unanswered: What factors determine the spatiotemporal evolution of deformable networks? Can we deliberately engineer the response of dynamic materials along a time-axis? How can we engineer energy barriers for the selective recognition of molecules? Answering these questions will require significant methodological development to understand structural dynamics across a range of time and length scales. P orous framework materials offer outstanding functionality due to their wide range of tuneable building blocks and ultrahigh porosity 1-5. The integration of functions, such as chemisorptive, redox, optically or catalytically active centers, encapsulated drugs, enzymes, nanoparticles, and more, has led to the discovery of metal-organic framework (MOF) applications in gas separation, CO 2 sequestration, gas storage, catalysis, optics, and sensing, and a roadmap for integration into electronic systems has even been proposed 6-12. The chemistry of three-dimensional (3D) porous framework materials, connecting nodes and linkers through a variety of chemical bonds is enormously rich 13,14. While decades ago, rationalization was aided by topology analysis and isoreticular expansion 15,16 , in the age of digitalization computer-aided design plays a crucial role in predicting millions of new 3D structures and their properties 17-19. The serendipitous discovery of an adsorption induced structural transformation in a network nowadays termed ELM-11 20 stimulated researchers and laid the foundations for exploring novel dynamic phenomena in porous frameworks. Like enzymes, structural changes are stimulated by guest molecules intruding into the porous frameworks leading to macroscopic volume changes of up to 200-300%. The adaptive change of pore size is a fascinating feature, but a selectivity comparable to that of enzymes has not been reached yet. Emerging applications of adaptive porous materials Porosity switching in the crystalline solid state represents a unique phenomenon observed only in a limited number of porous materials 21-25. This flexibility was predicted in 1998 for MOFs by Kitagawa and coworkers, and later termed "3 rd Generation MOFs" 25-27. These materials are characterized by dynamic features of the framework structure and are also named "soft porous crystals" (SPCs). We briefly account here a few remarkable applications of the dynamic frameworks reported today as the premise for our following perspective (Fig. 1). In gas storage applications, the pore closing upon desorption provides almost ideal deliverable capacity, a key advantage compared with rigid adsorbents 28. More importantly, for gas separations, the selective response of the porous host in adapting the pore shape to a reco...

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“…2D MOFs with expanded π‐conjugated structures of this kind currently possess good conductivity. [ 81–83 ] The enhanced p–π orbital coupling can promote the charge carriers transport within the 2D conjugated planes. The through‐space approach promotes the charge movement through noncovalent interactions (such as π–π interaction) of electroactive fragments in MOFs.…”

Section: The Mechanism and Characterization Of Electrical Conductivitmentioning

confidence: 99%

“…Based on this, many conductive 2D MOFs were reported and explored. [ 81 ] In a previous study, Kambe et al designed and synthesized nickel bis(dithiolene) complexes with π‐conjugated structure through a bottom‐up method ( Figure a). [ 52 ] The atomic force microscopy and scanning tunneling microscopy data illustrated their layered structures.…”

Section: The Design and Synthesis Of Conductive Mofsmentioning

confidence: 99%

Conductive Metal–Organic Frameworks: Design, Synthesis, and Applications

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fabricated. Combined with controlled synthesis, MOF materials are endowed with abundant various of structures, morphologies, and properties. [8-11] In addition, the as-prepared MOFs can be artificially modified via postsynthetic approaches utilizing their available pores and active sites of metal clusters or linkers. [12,13] As a result, not only the number of MOFs is further increased but also many interesting properties, such as high specific surface areas, tailorable pore sizes, modifiable structures, and properties are endowed with MOFs, which make them become potential candidates in storage/separation, catalysis, sensing, etc. [14,15] Another important application of MOFs is that they can act as conductive materials for electrocatalysis, sensing, and energy conversion, etc. [16-19] The existence of quantitative amounts of active metal centers, permanent porosity, and structural rigidity can facilitate surface contact and mass transfer as well as increase catalysis stability, making MOFs as ideal electrocatalysts. [20-22] In addition, they possess high specific surface areas, tunable bandgaps, and good charge transport properties, which extend their applications in sensing and energy storage. [23] Besides, the morphologies and characteristics of MOFs can be artificially modified to form 1D, 2D, or 3D structures via liquid phase selfassembly, physical/chemical exfoliation, layer-by-layer assembly, etc., promoting their applications in electrochemical devices and electronics. [24-26] With further structural design through postsynthesized modification, the performances of MOFs can be largely improved, facilitating their applications as conductive materials. [27-29] However, most MOFs are intrinsically electrically insulated, which seriously hinders their electrochemical applications. [29] The connected rigid metal ions and redox-inactive organic ligands increase the energy barrier for electron transfer, making them as electrical insulators. To overcome the drawbacks of MOFs, many feasible strategies have been adopted to promote the electron transfer in the structures of MOFs. [27,30-32] The high electrical conductivity of MOFs can be realized by integrating the conjugated planes or 1D chains in the structures, which relies on particular structural designs. [33-37] The conductivity of the MOFs can also be increased via doping with guest Metal-organic frameworks (MOFs) have aroused worldwide interest over the last two decades due to their various excellent properties, such as porosity, modifiability, stability, etc. Based on these unique features, they have been widely exploited for applications from electrocatalysis to electrochemical devices. However, most MOFs are inherently insulated due to the lack of free charge carriers and low-energy barriers for charge transfer, which largely restricts their further electrochemical applications. By imparting MOFs with electrical conductivity, their electrochemical process and catalysis efficiency can be effectively improved. Similarly, their applications in sensors, secon...

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Reversible redox switching of magnetic order and electrical conductivity in a 2D manganese benzoquinoid framework

Abstract: We report a 2D manganese benzoquinoid network that undergoes simultaneous redox switching of magnetic order and electrical conductivity.

Cited by 75 publications

References 83 publications

Crystallographic characterization of the metal–organic framework Fe₂(bdp)₃ upon reductive cation insertion

Crystallographic characterization of the metal–organic framework Fe₂(bdp)₃ upon reductive cation insertion

Four-dimensional metal-organic frameworks

Conductive Metal–Organic Frameworks: Design, Synthesis, and Applications

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Reversible redox switching of magnetic order and electrical conductivity in a 2D manganese benzoquinoid framework

Abstract: We report a 2D manganese benzoquinoid network that undergoes simultaneous redox switching of magnetic order and electrical conductivity.

Cited by 75 publications

References 83 publications

Crystallographic characterization of the metal–organic framework Fe2(bdp)3 upon reductive cation insertion

Crystallographic characterization of the metal–organic framework Fe2(bdp)3 upon reductive cation insertion

Four-dimensional metal-organic frameworks

Conductive Metal–Organic Frameworks: Design, Synthesis, and Applications

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Crystallographic characterization of the metal–organic framework Fe₂(bdp)₃ upon reductive cation insertion

Crystallographic characterization of the metal–organic framework Fe₂(bdp)₃ upon reductive cation insertion