Rajat Saha, Kajal Gupta, and Carlos J. Gomez Garcia · Crystal Growth & Design · 2024
Compare strategies used to improve electronic conductivity in MOFs by organising intrinsic framework-modulation routes and extrinsic guest/composite routes around charge-transport pathways, measurement methods, material families, thin-film fabrication, applications and remaining barriers.
The review’s argument is preserved as a navigable set of section summaries.
Reviews charge storage, electrocatalysis, sensors and devices, then distils major barriers: too few high-conductivity MOFs, weak composite interfaces, limited stability, incomplete mechanism assignment and application-specific performance gaps.
Relevance: Core · 2257 · 6. Challenges and Perspectives
Treats carbon/polymer/MOF hybrids as a separate route to bulk conductivity, with emphasis on physical mixtures versus growth on conductive substrates.
Relevance: Supporting · 2251 · 3. MOF Composites · Table 12
Classifies guest-mediated conductivity as metal-based guests, molecular guests and organic conducting polymer guests, including in situ and post-synthetic incorporation.
Relevance: Core · 2248 · 2.2 Extrinsically Conducting MOFs · Table 9
Organises intrinsic conductivity enhancement through redox-active ligands, extended conjugation, hard/soft donor atom matching, mixed-valence metal ions, metal electronic structure/cation size and pi-stacking interactions.
Relevance: Core · 2238 · 2.1 Intrinsically Conducting MOFs
Frames conductive MOFs as hybrid organic-inorganic materials whose practical deployment is limited by low conductivity; introduces two- and four-probe measurement geometries and cautions about mobility, carrier density and contact effects.
Relevance: Core · 2236 · 1.1 Conductivity Measurements · Figure 2
Distinguishes band-like and hopping mechanisms, then classifies MOF transport pathways as through-bond, through-plane/layer, through-space, redox hopping and through-guest.
Relevance: Core · 2238 · 1.3 Conduction Pathways · Figure 5
Summarises liquid- and gas-phase routes for conductive MOF thin films, including exfoliation, drop casting, layer-by-layer growth, interfacial growth and electrochemical/electrophoretic deposition.
Relevance: Core · 2253 · 4. Thin Film Fabrication of MOFs
Classification systems are attributed to this review and are not treated as a global material registry.
Guest-mediated conductivity is separated by whether the inserted species provides metal-based transport, redox/donor-acceptor molecular transport or polymer-chain transport.
Categories: metal ions and metal nanoclusters · organic, inorganic and organometallic molecules · organic conducting polymers
2236 · Introduction · Figure 1
Intrinsic conductivity occurs through the framework metal-ligand backbone; extrinsic conductivity occurs through guest species incorporated in the host framework.
Categories: intrinsically conducting MOFs · extrinsically conducting MOFs
2236 · Introduction · Figure 1
Summarises the review's intrinsic routes to improve orbital overlap, carrier density and delocalisation within the framework.
Categories: soft donor atoms · redox-active noninnocent ligands · extended pi-conjugated skeletons · mixed-valence metal centres · electron-rich metals
2236 · Introduction
Provides the core pathway language for Chapter 1, linking orbital overlap, pi-pi contacts, redox-active sites and guests to transport routes.
Categories: through-bond · through-plane · through-space · redox hopping · through-guest
2238 · 1.3 Conduction Pathways · Figure 5
Classifies thin-film fabrication by liquid- versus gas-phase methods, with frequently used sub-routes listed for device-relevant MOF films.
Categories: liquid-phase fabrication · gas-phase fabrication · exfoliation · drop-cast · interfacial method · electrochemical deposition · layer-by-layer growth
2253 · 4. Thin Film Fabrication of MOFs
The review separates delocalised band transport from localised hopping/tunnelling descriptions and highlights VRH dimensionality exponents for interpreting temperature-dependent conductivity.
Categories: band-like charge transport · redox hopping · variable range hopping · tunnelling model · superlocalization model
2237 · 1.2 Conducting Mechanisms · Figure 4
Review-defined families retain their representative materials and conduction descriptions.
S-rich dithiolene/benzenehexathiol based 2D or 3D frameworks with strong metal-sulfur orbital overlap.
Conduction: Strong metal-sulfur bonding, pi-d conjugation, redox control and interlayer packing produce some of the highest review-reported conductivity values.
Representative materials: Ag3BHT2 · Au3BHT2 · [Ag5(BHT)]n · [Cu3(BHT)]n · Ni3(BHT)2
Nodes / linkers: Ag · Au · Cu · Ni · Pd · benzenehexathiolate · metal dithiolene
2243 · S-Based Ligands · Table 5
MOFs combined with graphene, reduced graphene oxide, carbon nanotubes, polyaniline or conductive substrates to improve bulk conductivity.
Conduction: Conductivity is often provided by the conducting matrix or interfacial network rather than the pristine MOF framework.
Representative materials: ZIF-8/RGO · ZIF-8/SWCNTs · HKUST-1/polyaniline/Pt · HKUST-1-graphene
Nodes / linkers: Zn · Cu · Co · ZIF-8 · HKUST-1 · metalloporphyrin MOF
2252 · 3. MOF Composites · Table 12
Porous MOFs incorporating molecular donors, acceptors or dopants such as BEDT-TTF, TCNQ, iodine or metallacarboranes.
Conduction: Guests change framework electron density or create guest-guest/host-guest conductive paths; conductivity gains can be large but depend on loading, ordering and host channels.
Representative materials: (BEDT-TTF)3[MnCr(oxalate)3] · TCNQ@HKUST-1 · I2@[Zn3(D,L-lac)2(pybz)2] · NiCB@NU-1000
Nodes / linkers: Mn · Cr · Cu · Zn · Zr · oxalate frameworks · HKUST-1 BTC · lactate-pyridylbenzoate · TBAPy
2250 · 2.2.2 Molecular Guests · Table 10
2D layered MOFs based on hexahydroxybenzene or hexahydroxytriphenylene-type linkers forming metal-catecholate sheets.
Conduction: Extended pi-d conjugation within planar sheets and interlayer transport produce anisotropic in-plane/out-of-plane conductivity.
Representative materials: Cu3(HHB)2 · Cu3(HHTP)2 · Cu3(HHTP)(HHB) · Co9(HHTP)4 · Ni9(HHTP)4
Nodes / linkers: Cu · Co · Ni · hexahydroxybenzene · hexahydroxytriphenylene
2240 · 2.1.2 Extended Conjugated Organic Ligands · Table 2
2D honeycomb frameworks built from HIB, HITP or related N-donor conjugated ligands.
Conduction: Layered slipped or near-eclipsed honeycomb motifs give metallic-like or high semiconducting conductivity, with strong relevance to electrodes, sensors and FETs.
Representative materials: Ni3(HIB)2 · Cu3(HIB)2 · Fe3(HIB)2 · Mn3(HIB)2 · Ni3(HITP)2
Nodes / linkers: Ni · Cu · Fe · Mn · Co · hexaiminobenzene · hexaiminotriphenylene · octaiminophthalocyanine
2242 · N-Donor Ligands · Table 4
Frameworks where variable metal oxidation states create redox pathways for electron transfer.
Conduction: Partial oxidation or mixed Fe/Cu valence lowers activation barriers and can raise conductivity by orders of magnitude.
Representative materials: Cu[Cu(pdt)2] · Fe2(BDT)3 · [Fe(tri)2(BF4)x] · Fe anilate frameworks
Nodes / linkers: Cu · Fe · pyrazinedithiolate · benzeneditetrazolate · triazolate · anilate
2246 · 2.1.4 Mixed-Valence Metal Ions · Table 6
Isomorphous M2(DOBDC) and M2(DSBDC) frameworks used to contrast hard O-donor and softer S-donor transport pathways.
Conduction: S-donor analogues improve donor-metal orbital energy matching and through-bond transport relative to O-donor analogues.
Representative materials: [Mn2(DOBDC)] · [Mn2(DSBDC)] · [Fe2(DOBDC)] · [Fe2(DSBDC)]
Nodes / linkers: Mn · Fe · DOBDC · DSBDC
2241 · 2.1.3 Use of Hard/Soft Donor Atoms · Table 3
MOF hosts containing PEDOT, PPy or PANI polymer chains in pores/channels or on surfaces.
Conduction: Polymer chains act as continuous conjugated pathways inside pores or interlayer spaces; excessive loading can shift polymer outside pores.
Representative materials: PEDOT@MIL-101(Cr) · PPy@UiO-66 · PEDOT@UiO-66 · PANI@MIL-101(Cr) · PANI@UiO-66
Nodes / linkers: Cr · Zr · Zn · Cd · MIL-101 · UiO-66 · lactate-pyridylbenzoate · NDC/PCA
2251 · 2.2.3 Organic Conducting Polymers Guests · Table 11
MOFs using noninnocent catechol/semiquinoid/benzoquinone-type ligands with multiple accessible oxidation states.
Conduction: Mixed-valence ligands and metal-ligand valence tautomerism provide hopping/delocalisation pathways; reduction can either enhance or suppress conductivity depending on mixed-valence retention.
Representative materials: (NBu4)2[Fe2(dhbq)3] · (Me2NH2)2[Fe2(C6O4Cl2)3] · (Me4N)2[Mn2(C6O4Cl2)3]
Nodes / linkers: Fe · Mn · 2,5-dihydroxybenzoquinone · chloranilate · bromanilate · semiquinoid ligands
2239 · 2.1.1 Incorporation of Redox-Active Ligands · Table 1
Review-level synthesis principles remain separate from primary-study recipes.
Use isostructural series to tune S...S distances, ligand redox hopping and band/VRH behaviour through the metal ion.
Claimed effects: Cation identity can change both magnitude and mechanism of conductivity.
Controlling variables: metal cation identity · ionic radius · electronic configuration · intermolecular contact distance
Representative materials: (H2NMe2)2[M2(C6O4Cl2)3] · M2(TTFTB)
Caveat: Requires genuinely isostructural comparisons; conductivity trends may combine electronic and packing effects.
2246 · 2.1.5 Electronic Structure and Size of Metal Ions · Table 7
Build planar 2D sheets from ligands such as HHB, HHTP, HIB, HITP and BHT to support in-plane conjugation and interlayer contacts.
Claimed effects: Extended conjugation facilitates charge transport and can yield high or metallic-like conductivity in selected 2D MOFs.
Controlling variables: linker core size · metal coordination geometry · layer stacking · measurement orientation · film or crystal morphology
Representative materials: Cu3(HHTP)2 · Ni3(HITP)2 · Ni3(HIB)2 · [Cu3(BHT)]n
Caveat: Conductivity is sensitive to stacking, film thickness, contact geometry and anisotropy; not every conjugated 2D framework is highly conductive.
2240 · 2.1.2 Extended Conjugated Organic Ligands · Table 2
Use partial oxidation/reduction or mixed-valence metal frameworks to create low-barrier electron-transfer pathways.
Claimed effects: Mixed-valence states can substantially increase conductivity and reduce activation barriers.
Controlling variables: metal oxidation state · air exposure or chemical oxidation · redox couple identity · activation energy
Representative materials: Fe2(BDT)3 · [Fe(tri)2(BF4)x] · Cu[Cu(pdt)2]
Caveat: Air oxidation or post-synthetic doping may complicate stability and phase/composition assignment.
2246 · 2.1.4 Mixed-Valence Metal Ions · Table 6
Use guest donors/acceptors such as BEDT-TTF, TCNQ or iodine to alter carrier density or add guest-mediated pathways in pores/interlayers.
Claimed effects: Can yield large conductivity increases while preserving porous host scaffolds.
Controlling variables: guest loading · guest ordering · donor-acceptor interaction · channel geometry · post-synthetic versus in situ incorporation
Representative materials: BEDT-TTF oxalate framework · TCNQ@HKUST-1 · I2@[Zn3(D,L-lac)2(pybz)2]
Caveat: The conductive pathway may be guest-dominated and not intrinsic framework transport; loading uniformity and stability need verification.
2250 · 2.2.2 Molecular Guests · Table 10
Design frameworks with aromatic ligands close enough to create interchain, interlayer or intraframework pi-pi transport routes.
Claimed effects: Pi-stacked motifs can provide through-space conduction pathways even when metal-ligand overlap is limited.
Controlling variables: aromatic plane distance · interpenetration · desolvation · packing geometry
Representative materials: [Cd(DPNDI)(OH2)4](NO3)1.3.nDMA · [ZnNa2(ABEDBA)2(DEF)2].DEF
Caveat: Through-space contributions may be difficult to disentangle from framework-derived transport and solvent effects.
2247 · 2.1.6 pi...pi Stacking Interactions · Table 8
Adsorb monomers into pores/channels and oxidatively polymerise them to form PEDOT, PPy or PANI pathways.
Claimed effects: Pore-confined conducting polymers can provide continuous conjugated pathways and dramatically raise conductivity over insulating hosts.
Controlling variables: monomer loading · oxidant/dopant · pore confinement · polymer location · host pore size
Representative materials: PEDOT@MIL-101(Cr) · PPy@UiO-66 · PANI@MIL-101(Cr)
Caveat: At high loading, polymers may cover surfaces rather than remain confined, so transport cannot automatically be assigned to internal MOF channels.
2251 · 2.2.3 Organic Conducting Polymers Guests · Table 11
Use ligands with accessible oxidation states and frontier orbitals matched to transition metals to create mixed-valence/hopping pathways.
Claimed effects: Can create efficient transport through ligand mixed valence and modulate conductivity by changing carrier density and mobility.
Controlling variables: ligand oxidation state · degree of reduction/oxidation · metal-ligand frontier orbital overlap · cation removal/insertion conditions
Representative materials: (NBu4)2[Fe2(dhbq)3] · (Me2NH2)2[Fe2(C6O4Cl2)3] · (Me4N)2[Mn2(C6O4Cl2)3]
Caveat: Reduction does not always improve conductivity; loss of mixed valence or added vacancies may reduce mobility.
2239 · 2.1.1 Incorporation of Redox-Active Ligands · Table 1
Replace hard donor motifs with softer S, Se or related donor atoms and pair them with suitable transition metals to increase covalency and orbital overlap.
Claimed effects: Better orbital energy matching increases charge delocalisation and through-bond conductivity.
Controlling variables: donor atom identity · metal oxidation state · metal d-orbital energy · M-X chain continuity
Representative materials: [Fe2(DSBDC)] · [Mn2(DSBDC)] · [Cu3(C6Se6)]n
Caveat: Soft donor substitution alone is insufficient if topology, metal identity or framework packing are unfavourable.
2241 · 2.1.3 Use of Hard/Soft Donor Atoms · Table 3
Use exfoliation, layer-by-layer, interfacial, electrochemical or electrophoretic methods to prepare MOF films on conductive or device substrates.
Claimed effects: Thin-film processing enables device integration and can control thickness, orientation and electrode contact quality.
Controlling variables: substrate functionalisation · film thickness · growth interface · deposition voltage · orientation and continuity
Representative materials: HKUST-1 films · Ni3(HITP)2 thin films · TCNQ@Cu-BTEC films
Caveat: Film measurements are sensitive to substrate, contacts and morphology; device performance does not necessarily prove bulk framework conductivity.
2253 · 4. Thin Film Fabrication of MOFs
These are the review authors’ synthesis, not newly measured results.
Conducting MOFs are promising for storage, electrocatalysis, sensors and electronics, but stability, scalability and high conductivity remain barriers to industrial use.
Evidence basis: review_reasoning
Caveat: Application-specific performance comparisons should be checked in primary studies before quantitative use.
2257 · 6. Challenges and Perspectives
MOF composites are limited by weak/nonuniform interactions between MOFs and conductive matrices when prepared by simple mixing.
Evidence basis: review_reasoning
Caveat: Direct synthesis of MOF nanoparticles inside functionalised matrices is proposed as a possible route, not yet a proven general solution.
2257 · 6. Challenges and Perspectives
The role of dimensionality in conductivity remains under-resolved because the review states no published examples of same-composition MOFs differing only in dimensionality.
Evidence basis: review_reasoning
Caveat: This is the review authors' state-of-literature judgement as of the review, not an independently verified systematic search.
2238 · 1.3 Conduction Pathways
The review's fundamental distinction is whether charge transport occurs through the MOF backbone or through guest species within the host.
Evidence basis: review_reasoning
Caveat: Some systems may involve coupled host-guest pathways rather than a clean binary split.
2236 · Introduction
In extrinsically conducting MOFs, incorporated guests form transport pathways through host-guest or guest-guest interactions; polymer guests provide continuous conjugated networks.
Evidence basis: review_reasoning
Caveat: The review does not establish the microscopic mechanism for every guest@MOF example.
2238 · 1.3 Conduction Pathways · Figure 5
The highest benchmark conductivities in the review cluster around planar, highly conjugated S- or N-donor frameworks, especially BHT/HIB/HITP-type 2D systems.
Evidence basis: multi_reference
Caveat: Numerical comparisons combine thin film, pellet and single-crystal measurements.
2257 · 6. Challenges and Perspectives
Low electrical conductivity is presented as the major handicap limiting electronic applications of most MOFs.
Evidence basis: review_reasoning
Caveat: The review also notes an increasing set of highly conducting and metallic examples.
2235 · Abstract
Four-probe, two-probe, four-point and van der Pauw methods are not interchangeable; their contact geometries and sample types shape conductivity interpretation.
Evidence basis: review_reasoning
Caveat: Benchmark tables mix pressed pellet, single-crystal and thin-film values, so comparisons need measurement-method qualifiers.
2236 · 1.1 Conductivity Measurements · Figures 2-3
Most MOFs are described as insulators or semiconductors, with metallic conductivity increasingly reported but still exceptional.
Evidence basis: review_reasoning
Caveat: Metallic labels rely on temperature-dependent transport and measurement quality in original studies.
2237 · 1.2 Conducting Mechanisms
Ligand mixed valence in semiquinoid/quinoid MOFs is interpreted as an efficient pathway to delocalised and tunable electronic structures.
Evidence basis: multi_reference
Caveat: Carrier mobility can decrease after some reductions; the direction of conductivity change depends on the redox chemistry.
2239 · 2.1.1 Incorporation of Redox-Active Ligands · Table 1
Matching soft donor atoms with suitable transition metals increases covalency and metal-ligand orbital overlap, improving through-bond conductivity.
Evidence basis: multi_reference
Caveat: This is a design principle; individual material behaviour still depends on topology, metal identity and packing.
2241 · 2.1.3 Use of Hard/Soft Donor Atoms
Transport mechanisms, carrier type, carrier density and mobility have been established only in a few conducting MOFs, limiting rational design.
Evidence basis: review_reasoning
Caveat: The review calls for combined experimental and theoretical studies rather than relying on conductivity magnitude alone.
2257 · 6. Challenges and Perspectives
Every row remains visibly secondary and links to a primary dossier only where the mapping is verified.
| Material | Property | Reported value | Context and quality | Primary evidence | Review source |
|---|---|---|---|---|---|
| Secondary(BEDT-TTF)3[MnCr(oxalate)3] | room-temperature electrical conductivity | 250 S cm-1 | Four-probe, within plane; metallic conductivity from 2-300 K; secondary benchmark from review Table 10/text. Table · Rounded Reported | research_0024 | 2249 · 2.2.2 Molecular Guests · Table 10 |
| Secondary[Cu3(BHT)]n | thin-film conductivity | 750-1580 S cm-1 | Four-probe on highly crystalline thin films prepared by liquid-liquid interface method. Table · Range | research_0006 | 2243 · S-Based Ligands · Table 5 |
| Secondary[Cu3(C6Se6)]n | pressed-pellet conductivity | ~110 S cm-1 at 300 K | Four-probe on pressed pellet; semiconducting behaviour from 10 to 400 K. Text · Approximate | No verified corpus mapping | 2246 · S-Based Ligands · Table 5; Figure 14 |
| SecondaryCu3(HHTP)2 hexagonal flakes | out-of-plane and in-plane conductivity | 1.5 S cm-1 out-of-plane; 0.5 S cm-1 in-plane | Four-probe on hexagonal flakes/single crystals; value_numeric records out-of-plane value. Table · Exact Reported | research_0005 | 2240 · 2.1.2 Extended Conjugated Organic Ligands · Table 2 |
| SecondaryFe2(BDT)3 after 30 days air exposure | electrical conductivity | 1.2 S cm-1 | Two-probe on single crystal; after 30 days exposure to air; activation energy 160 meV. Table · Exact Reported | research_0221 | 2246 · 2.1.4 Mixed-Valence Metal Ions · Table 6 |
| Secondary(Me2NH2)2[Fe2(C6O4Cl2)3].2H2O.6DMF | room-temperature conductivity | 1.4 x 10-2 S cm-1 | Oxidized two-dimensional MOF; table reports two-probe on pressed pellets. Table · Exact Reported | research_0095 | 2239 · 2.1.1 Incorporation of Redox-Active Ligands · Table 1 |
| Secondary(NBu4)2[Fe2(dhbq)3] | electrical conductivity | 0.16 S cm-1 | 298 K; two-probe DC on pressed pellets; oxidized form. Table · Exact Reported | research_0186 | 2239 · 2.1.1 Incorporation of Redox-Active Ligands · Table 1 |
| Secondary[Fe2(DSBDC)] | electrical conductivity | 3.9 x 10-6 S cm-1 | Two-probe on pressed pellets; S-donor MOF-74 analogue. Table · Exact Reported | research_0063 | 2241 · 2.1.3 Use of Hard/Soft Donor Atoms · Table 3 |
| SecondaryFe3(HIB)2 | electrical conductivity | 150 S cm-1 | Van der Pauw on pressed pellet per Table 4 footnote. Table · Exact Reported | No verified corpus mapping | 2242 · N-Donor Ligands · Table 4 |
| SecondaryTCNQ@HKUST-1 | thin-film conductivity | 7 x 10-2 S cm-1 from parent 10-8 S cm-1 | Thin film; TCNQ guest incorporated by soaking; secondary review Table 10/text. Table · Exact Reported | research_0088 | 2249 · 2.2.2 Molecular Guests · Table 10; Figure 20 |
| SecondaryI2@[Zn3(D,L-lac)2(pybz)2].2.5DMF | anisotropic guest@MOF conductivity | 3.42 x 10-3 S cm-1 along channels; 1.65 x 10-4 S cm-1 perpendicular | Iodine loaded in 1D channels; value_numeric records along-channel conductivity. Text · Exact Reported | No verified corpus mapping | 2250 · 2.2.2 Molecular Guests · Table 10; Figure 21 |
| SecondaryNi3(BHT)2 oxidized nanosheet | electrical conductivity | 160 S cm-1 | Four-probe van der Pauw, oxidized sample; review notes method avoids grain-boundary/contact artefacts. Table · Exact Reported | research_0361 | 2243 · S-Based Ligands · Table 5; Figure 12 |
| SecondaryNi3(HIB)2 | electrical conductivity | 0.7-10 S cm-1 | Van der Pauw on pressed pellet; range reported by review Table 4. Table · Range | No verified corpus mapping | 2242 · N-Donor Ligands · Table 4 |
| SecondaryNi3(HITP)2 | single-crystal conductivity | ~150 S cm-1 at 295 K | Single crystals; two- and four-probe according to Table 4; nonzero conductivity at 0.3 K. Text · Approximate | research_0005 | 2241 · N-Donor Ligands · Table 4 |
| Secondary20% PANI@MIL-101(Cr) | guest@MOF conductivity | 0.55 S cm-1 | 20% PANI loading; impedance on pressed pellet per Table 11. Table · Exact Reported | No verified corpus mapping | 2251 · 2.2.3 Organic Conducting Polymers Guests · Table 11; Figure 26 |
| Secondary(H2NMe2)2[V2(C6O4Cl2)3] | room-temperature conductivity | 0.45 S cm-1 | Two-probe under Ar; V-containing semiquinoid framework; VRH mechanism noted by review. Table · Exact Reported | No verified corpus mapping | 2247 · 2.1.5 Electronic Structure and Size of Metal Ions · Table 7 |
| SecondaryZIF-8/RGO (20 wt%) | composite conductivity | 0.64 S cm-1 | Four-probe on pressed pellets; composite with 20 wt% graphene. Table · Exact Reported | No verified corpus mapping | 2252 · 3. MOF Composites · Table 12 |
Open questions are presented as review-author priorities, not conclusions from the primary database.
For charge-storage MOFs, uptake/release of metal ions and correlation between storage and active sites are insufficiently resolved.
Proposed direction: Study ion transport, active sites and charge-discharge processes in detail for high capacity and recyclability.
2257 · 6. Challenges and Perspectives
MOF-composite conductivity is limited by nonuniformity and weak MOF/conducting-matrix interactions in simple mixtures.
Proposed direction: Directly synthesise MOF nanoparticles inside functionalised conducting matrices to strengthen interfacial charge transfer and stability.
2257 · 6. Challenges and Perspectives
The review notes a lack of same-composition conductive MOF polymorphs with different dimensionalities, preventing clean isolation of dimensionality effects.
Proposed direction: Prepare polymorphic conducting MOFs differing only in dimensionality to test through-bond, through-plane and through-space contributions.
2238 · 1.3 Conduction Pathways
There are still very few MOFs reported with conductivities above 1 S cm-1, while most electronic applications require high conductivity.
Proposed direction: Explore donor atoms beyond common S/N systems, alternative transition metals and radical/redox-active ligands to expand the set of high-conductivity frameworks.
2257 · 6. Challenges and Perspectives
Charge transport mechanisms, carrier type, carrier density and mobility are established only in a few intrinsically and extrinsically conducting MOFs.
Proposed direction: Combine temperature-dependent transport, mobility/carrier-density measurements and theoretical modelling to assign mechanisms before application optimisation.
2257 · 6. Challenges and Perspectives
Most highly conducting 2D MOFs have square-planar metal centres with axial vacancies that may reduce stability under solvent/electrochemical conditions.
Proposed direction: Design strong metal-ligand coordination environments while preserving conductivity.
2257 · 6. Challenges and Perspectives
Mappings show which printed review references have a verified counterpart in the frozen primary corpus.
| Reference | Study | Role and context | Corpus mapping |
|---|---|---|---|
| Ref. 352000 | Coexistence of ferromagnetism and metallic conductivity in a molecule-based layered compound | historical_benchmark · extrinsic_guest_benchmarkUsed by the review as an early host-guest conductive MOF/coordination framework example with metallic conductivity and magnetic ordering. | research_0024 |
| Ref. 382009 | Electroconductive Porous Coordination Polymer Cu-[Cu(Pdt)2] Composed of Donor and Acceptor Building Units | mixed_valence_benchmark · sulfur_ligand_benchmarkUsed as an early mixed-valence and thiol-based conducting MOF benchmark. | research_0201 |
| Ref. 532014 | Redox Control and High Conductivity of Nickel Bis(Dithiolene) Complex pi-Nanosheet: A Potential Organic Two-Dimensional Topological Insulator | redox_control_benchmark · high_conductivity_benchmarkSupports the review's discussion of oxidation-state tuning in a nickel bis(dithiolene) nanosheet. | research_0361 |
| Ref. 582015 | A two-dimensional pi-d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour | high_conductivity_benchmark · sulfur_ligand_benchmarkUsed for the review's highest-conductivity MOF benchmark in BHT-based thin films. | research_0006 |
| Ref. 642017 | 2D Conductive Iron-Quinoid Magnets Ordering up to Tc = 105 K via Heterogenous Redox Chemistry | redox_active_ligand_benchmarkUsed to compare oxidized and reduced iron chloranilate MOF conductivities and mixed-valence loss. | research_0095 |
| Ref. 662015 | Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal-Organic Framework | redox_active_ligand_benchmark · mixed_valence_benchmarkUsed to show oxidized ferric semiquinoid MOF is more conductive than its reduced form. | research_0186 |
| Ref. 762019 | Single Crystals of Electrically Conductive 2D MOFs: Structural and Electrical Transport Properties | single_crystal_transport · anisotropy_benchmarkUsed for single-crystal/flake conductivity benchmarks in 2D conductive MOFs. | research_0005 |
| Ref. 802015 | Million-Fold Electrical Conductivity Enhancement in Fe2(DEBDC) versus Mn2(DEBDC) (E = S, O) | soft_donor_benchmark · structure_property_linkUsed for O/S donor atom and Fe/Mn comparisons in MOF-74 analogues. | research_0063 |
| Ref. 832017 | Signature of Metallic Behavior in the Metal-Organic Frameworks M3(hexaiminobenzene)2 (M = Ni, Cu) | n_donor_benchmark · metallic_behaviourUsed for metallic-like N-donor 2D MOF conductivity ranges. | Unmapped |
| Ref. 852019 | Unveiling Dual-Linkage 3D Hexaiminobenzene Metal-Organic Frameworks towards Long-Lasting Advanced Reversible Zn-Air Batteries | n_donor_benchmark · applications_contextUsed by the review for very high HIB-family conductivity values in Fe and Mn derivatives. | Unmapped |
| Ref. 1012019 | [Cu3(C6Se6)]n: The First Highly Conductive 2D pi-d Conjugated Coordination Polymer Based on Benzenehexaselenolate | selenium_donor_benchmark · high_conductivity_benchmarkUsed for the Se-donor strategy and high pressed-pellet conductivity. | Unmapped |
| Ref. 1052017 | Is iron unique in promoting electrical conductivity in MOFs? | mixed_valence_benchmark · air_oxidation_benchmarkUsed to show air oxidation of Fe2(BDT)3 increases conductivity by forming mixed-valence states. | research_0221 |
| Ref. 1082018 | Control of Electronic Structure and Conductivity in Two-Dimensional Metal-Semiquinoid Frameworks of Titanium, Vanadium, and Chromium | electronic_structure_benchmark · mechanism_benchmarkUsed to show metal identity changes both conductivity magnitude and mechanism in isostructural semiquinoid frameworks. | Unmapped |
| Ref. 1122019 | Porous Molecular Conductor: Electrochemical Fabrication of Through-Space Conduction Pathways among Linear Coordination Polymers | pi_stacking_benchmark · through_space_transportUsed for pi-stacked DPNDI through-space conduction and desolvation-enhanced conductivity. | research_0326 |
| Ref. 1222014 | Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices | molecular_guest_benchmark · thin_film_deviceUsed for TCNQ guest incorporation in HKUST-1 thin-film devices and large conductivity increase. | research_0088 |
| Ref. 1282010 | 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 | iodine_guest_benchmark · anisotropy_benchmarkUsed for iodine-loaded MOF channel conductivity and anisotropy. | Unmapped |
| Ref. 1382016 | Nanostructuration of PEDOT in Porous Coordination Polymers for Tunable Porosity and Conductivity | polymer_guest_benchmarkUsed for PEDOT@MIL-101(Cr) polymer guest conductivity enhancement. | Unmapped |
| Ref. 1392020 | Imparting Multifunctionality by Utilizing Biporosity in a Zirconium-Based Metal-Organic Framework | polymer_guest_benchmarkUsed for polymer insertion into UiO-66 pores and comparison with physical mixtures. | Unmapped |
| Ref. 1422018 | Hierarchical porous PANI/MIL-101 nanocomposites based solid-state flexible supercapacitor | polymer_guest_benchmark · applications_contextUsed for PANI loading in MIL-101(Cr) and conductivity maximum at 20% loading. | Unmapped |
| Ref. 1462016 | Graphene/ZIF-8 composites with tunable hierarchical porosity and electrical conductivity | composite_benchmarkUsed as a graphene/MOF composite benchmark for conductivity enhancement. | Unmapped |
| Ref. 1562017 | Porous Field-Effect Transistors Based on a Semiconductive Metal-Organic Framework | thin_film_device · fet_benchmarkUsed in thin-film fabrication and device sections for gas-liquid interface grown Ni3(HITP)2 FETs. | research_0015 |
| Ref. 2292017 | Porous Field-Effect Transistors Based on a Semiconductive Metal-Organic Framework | fet_benchmark · thin_film_deviceUsed for a porous FET benchmark based on highly conducting Ni3(HITP)2 thin films. | research_0015 |