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Title: Electrically Conductive Metal–Organic Frameworks

Abstract

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.

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); US Army Research Office (ARO); National Science Foundation (NSF)
OSTI Identifier:
1615048
Alternate Identifier(s):
OSTI ID: 1657167; OSTI ID: 1769039
Grant/Contract Number:  
SC0018235
Resource Type:
Published Article
Journal Name:
Chemical Reviews
Additional Journal Information:
Journal Name: Chemical Reviews Journal Volume: 120 Journal Issue: 16; Journal ID: ISSN 0009-2665
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Metals; Metal organic frameworks; Charge transport; Electrical conductivity; Materials

Citation Formats

Xie, Lilia S., Skorupskii, Grigorii, and Dincă, Mircea. Electrically Conductive Metal–Organic Frameworks. United States: N. p., 2020. Web. doi:10.1021/acs.chemrev.9b00766.
Xie, Lilia S., Skorupskii, Grigorii, & Dincă, Mircea. Electrically Conductive Metal–Organic Frameworks. United States. https://doi.org/10.1021/acs.chemrev.9b00766
Xie, Lilia S., Skorupskii, Grigorii, and Dincă, Mircea. Fri . "Electrically Conductive Metal–Organic Frameworks". United States. https://doi.org/10.1021/acs.chemrev.9b00766.
@article{osti_1615048,
title = {Electrically Conductive Metal–Organic Frameworks},
author = {Xie, Lilia S. and Skorupskii, Grigorii and Dincă, Mircea},
abstractNote = {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.},
doi = {10.1021/acs.chemrev.9b00766},
journal = {Chemical Reviews},
number = 16,
volume = 120,
place = {United States},
year = {2020},
month = {4}
}

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Porous Scaffolds for Electrochemically Controlled Reversible Capture and Release of Ethylene
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π-Conjugated Nickel Bis(dithiolene) Complex Nanosheet
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Coordination compounds of 1,4-dihydroxybenzoquinone and its homologues. Structures and properties
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3-D Coordination Polymers Based on the Tetrathiafulvalenetetracarboxylate (TTF-TC) Derivative: Synthesis, Characterization, and Oxidation Issues
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High temperature ferromagnetism in π-conjugated two-dimensional metal–organic frameworks
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Tetrathiafulvalenes as building blocks in supramolecular chemistry II
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An electroactive porous network from covalent metal–dithiolene links
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Facile synthesis and characterization of trimesic acid-Cu based metal organic frameworks
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Immobilizing Molecular Metal Dithiolene-Diamine Complexes on 2D Metal-Organic Frameworks for Electrocatalytic H 2 Production
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High-mobility band-like charge transport in a semiconducting two-dimensional metal–organic framework
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Buckled two-dimensional Xene sheets
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Base-Induced Formation of Two Magnesium Metal-Organic Framework Compounds with a Bifunctional Tetratopic Ligand
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Tunability of electronic band gaps from semiconducting to metallic states via tailoring Zn ions in MOFs with Co ions
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Charge Delocalization and Bulk Electronic Conductivity in the Mixed-Valence Metal–Organic Framework Fe(1,2,3-triazolate) 2 (BF 4 ) x
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Nanosheets of Two-Dimensional Magnetic and Conducting Fe(II)/Fe(III) Mixed-Valence Metal–Organic Frameworks
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Charge Transport in Organic Semiconductors
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Conducting π-Conjugated Bis(iminothiolato)nickel Nanosheet
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A Dual‐Ligand Porous Coordination Polymer Chemiresistor with Modulated Conductivity and Porosity
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Origin of the Chemiresistive Response of Ultrathin Films of Conductive Metal–Organic Frameworks
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Electronics and optoelectronics of two-dimensional transition metal dichalcogenides
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Seebeck Coefficient Measurements of Polycrystalline and Highly Ordered Metal-Organic Framework Thin Films
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Two-Dimensional π -Conjugated Covalent-Organic Frameworks as Quantum Anomalous Hall Topological Insulators
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Substituted Quinodimethans. II. Anion-radical Derivatives and Complexes of 7,7,8,8-Tetracyanoquinodimethan
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Single Crystals of Electrically Conductive Two-Dimensional Metal–Organic Frameworks: Structural and Electrical Transport Properties
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High Charge Carrier Mobility in Two Dimensional Indium (III) Isophthalic Acid Based Frameworks
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Metal Azolate Frameworks: From Crystal Engineering to Functional Materials
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Prospects for electroactive and conducting framework materials
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Doping of metal–organic frameworks towards resistive sensing
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Conductive Metal-Organic Framework Nanowire Array Electrodes for High-Performance Solid-State Supercapacitors
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Graphene-like metal–organic frameworks: morphology control, optimization of thin film electrical conductivity and fast sensing applications
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Two-Dimensional Metal–Organic Surfaces for Efficient Hydrogen Evolution from Water
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Metal bis-1,2-dithiolene complexes in conducting or magnetic crystalline assemblies
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Coordination-induced reversible electrical conductivity variation in the MOF-74 analogue Fe 2 (DSBDC)
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The Chemistry and Applications of Metal-Organic Frameworks
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Conductivity, Doping, and Redox Chemistry of a Microporous Dithiolene-Based Metal−Organic Framework
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Cation exchange at the secondary building units of metal–organic frameworks
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Efficient and tunable one-dimensional charge transport in layered lanthanide metal–organic frameworks
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Measuring and Reporting Electrical Conductivity in Metal–Organic Frameworks: Cd 2 (TTFTB) as a Case Study
journal, October 2016

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New Porous Crystals of Extended Metal-Catecholates
journal, August 2012

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Charge Transfer-Induced Molecular Hole Doping into Thin Film of Metal–Organic Frameworks
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Electrically Conductive Porous Metal-Organic Frameworks
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Chemical principles for electroactive metal–organic frameworks
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Rigid Pillars and Double Walls in a Porous Metal-Organic Framework: Single-Crystal to Single-Crystal, Controlled Uptake and Release of Iodine and Electrical Conductivity
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Intrinsically conducting metal–organic frameworks
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Theoretical Evidence for the Singlet Diradical Character of Square Planar Nickel Complexes Containing Two o -Semiquinonato Type Ligands
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