Coordination-induced reversible electrical conductivity variation in the MOF-74 analogue Fe<sub>2</sub>(DSBDC)

Sun, Lei; Hendon, Christopher H.; Dincă, Mircea

doi:10.1039/c8dt02197j

Cited by 27 publications

(23 citation statements)

References 38 publications

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“…This difference was hypothesized to be the result of defects introduced by the solvent exchange and evacuation process. Removal of coordinated DMF in Fe 2 (DSBDC) was found to further reduce 115 the conductivity by an additional 2 orders of magnitude to 1.5 × 10 –9 S/cm. DFT calculations indicated that coordinated DMF accepts electron density from Fe centers, effectively hole-doping the material and increasing charge density.…”

Section: Through-bond Pathwaysmentioning

confidence: 99%

Electrically Conductive Metal–Organic Frameworks

2020

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Metal–organic frameworks (MOFs) are intrinsically porous extended solids formed by coordination bonding between organic ligands and metal ions or clusters. High electrical conductivity is rare in MOFs, yet it allows for diverse applications in electrocatalysis, charge storage, and chemiresistive sensing, among others. In this Review, we discuss the efforts undertaken so far to achieve efficient charge transport in MOFs. We focus on four common strategies that have been harnessed toward high conductivities. In the “through-bond” approach, continuous chains of coordination bonds between the metal centers and ligands’ functional groups create charge transport pathways. In the “extended conjugation” approach, the metals and entire ligands form large delocalized systems. The “through-space” approach harnesses the π–π stacking interactions between organic moieties. The “guest-promoted” approach utilizes the inherent porosity of MOFs and host–guest interactions. Studies utilizing less defined transport pathways are also evaluated. For each approach, we give a systematic overview of the structures and transport properties of relevant materials. We consider the benefits and limitations of strategies developed thus far and provide an overview of outstanding challenges in conductive MOFs.

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Section: Through-bond Pathwaysmentioning

confidence: 99%

Electrically Conductive Metal–Organic Frameworks

2020

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“…The localized charges with discrete energy levels hop between favorable neighboring units. For instance, M 2 (DOBDC) (M = Mn 2+ , Fe 2+ ) 12 and Fe‐MOF‐74 11 both rely on the hopping of specific site charges. The through‐space conduction also depends on the charge transport between the donor and the acceptor.…”

Section: Structural and Electronic Characteristics Of Conductive Mofsmentioning

confidence: 99%

Conductive metal‐organic frameworks: Recent advances in electrochemical energy‐related applications and perspectives

et al. 2020

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Metal‐organic frameworks (MOFs), typically constructed with metallic nodes and organic linkers, have influenced the development of modular solid materials. Their adjustable molecular structure provides a remarkable variety of MOF‐based solid‐state structures towards diverse applications. However, the low conductivity of traditional MOFs extremely hinders their applications in electronic and electrochemical devices. The emerging conductive MOFs, generally possessing two‐dimensional layered structures, are endowed with both the structural merits of common MOFs and exceptional electronic/ionic conductivities. Besides, the selection and optimization of ligands and metal centers, as well as synthetic methods enormously affects the intrinsic conductivity of conductive MOFs. The distinctive crystal structures and superb conductivity promise their appealing applications in electrochemical energy‐related fields. In the review, we mainly summarize representative crystal features, conducting mechanisms and recent advances in rational design and synthesis of conductive MOFs, along with their versatile applications as electrodes for electrochemical capacitors and rechargeable batteries, and as catalysts towards electrocatalysis. Finally, the involved challenges and future trends/prospects of the conductive MOFs for electrochemical energy‐related applications are further proposed.

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“…The use of hard or borderline Lewis acids, such as zirconium(IV) or zinc(II), with linkers possessing thioether groups ortho to the dicarboxylate donors typically leads to the formation of UiO [ 32 ] or IRMOF structure types [ 33 ], in which the sulfur donors are not employed due to the coordination mismatch. For the mercapto-containing linker 2,5-dimercaptobenzene dicarboxylic acid (DMBDC), MOF-74, and UiO analogues were prepared with Fe and Zr as the metals, respectively [ 34 , 35 ]. In the case of the 2,5-bis(allylsulfanyl)benzene dicarboxylic acid (ASBDC) linker, we reasoned that the use of silver(I) as a metal node, with its coordination preference for soft thioether donors, might lead to more highly coordinated silver centers and a stable structure.…”

Section: Resultsmentioning

confidence: 99%

A Stable Coordination Polymer Based on Rod-Like Silver(I) Nodes with Contiguous Ag-S Bonding

2020

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Silver(I)-based coordination polymers or metal-organic frameworks (MOFs) display useful antibacterial properties, whereby distinct materials with different bonding can afford control over the release of silver(I) ions. Such silver(I) materials are comprised of discrete secondary building units (SBUs), and typically formed with ligands possessing only soft or borderline donors. We postulated that a linker with four potential donor groups, comprising carboxylate and soft thioether donors, 2,5-bis (allylsulfanyl) benzene dicarboxylic acid (ASBDC), could be used to form stable, highly connected coordination polymers with silver(I). Here, we describe the synthesis of a new material, (Ag2(ASBDC)), which possesses a rod-like metal node-based 3D honeycomb structure, strongly -stacked linkers, and steric bulk to protect the node. Due to the rod-like metal node and the blocking afforded by the ordered allyl groups, the material displays notable thermal and moisture stability. An interesting structural feature of (Ag2(ASBDC)) is contiguous Ag–S bonding, essentially a helical silver chalcogenide wire, which extends through the structure. These interesting structural features, coupled with the relative ease by which MOFs made with linear dicarboxylate linkers can be reticulated, suggests this may be a structure type worthy of further investigation.

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Coordination-induced reversible electrical conductivity variation in the MOF-74 analogue Fe₂(DSBDC)

Abstract: DMF coordination to Fe centers induces partial electron transfer and improves electrical conductivity in Fe2(DSBDC) by three orders of magnitude.

Cited by 27 publications

References 38 publications

Electrically Conductive Metal–Organic Frameworks

Electrically Conductive Metal–Organic Frameworks

Conductive metal‐organic frameworks: Recent advances in electrochemical energy‐related applications and perspectives

A Stable Coordination Polymer Based on Rod-Like Silver(I) Nodes with Contiguous Ag-S Bonding

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Coordination-induced reversible electrical conductivity variation in the MOF-74 analogue Fe2(DSBDC)

Abstract: DMF coordination to Fe centers induces partial electron transfer and improves electrical conductivity in Fe2(DSBDC) by three orders of magnitude.

Cited by 27 publications

References 38 publications

Electrically Conductive Metal–Organic Frameworks

Electrically Conductive Metal–Organic Frameworks

Conductive metal‐organic frameworks: Recent advances in electrochemical energy‐related applications and perspectives

A Stable Coordination Polymer Based on Rod-Like Silver(I) Nodes with Contiguous Ag-S Bonding

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Product

Resources

About

Coordination-induced reversible electrical conductivity variation in the MOF-74 analogue Fe₂(DSBDC)