Akashdeep Nath, K. S. Asha, and Sukhendu Mandal · Chemistry-A European Journal · 2021
Review conductive MOFs from electronic-structure fundamentals through design strategies, measurement techniques, spectroelectrochemistry, and electrochemical applications.
The review’s argument is preserved as a navigable set of section summaries.
Connects conductive MOF transport to capacitors, batteries, electrocatalysis, and sensing, with emphasis on why conductivity matters for devices.
Relevance: Supporting · 11522 · 11. Electrochemical Applications
Distils chemical design logic into through-bond, through-space, and hopping approaches and cautions against overassigning mechanisms from polycrystalline data.
Relevance: Core · 11487 · 3. Design Strategy · Figure 5
Organises conductive MOFs with extended conjugation into tetraoxolene, semiquinoid, thiolate, imino, and selenol ligand families.
Relevance: Core · 11499 · 6. Extended Conjugation · Figure 15
Summarises iodine, TCNQ, fullerene, polymer, and oxide incorporation as post-synthetic ways to alter electronic structure and conductivity.
Relevance: Core · 11517 · 9. Guest Incorporated Conductivity · Figure 33
Frames conductive MOFs as a transition from classical porous materials toward electronic and electrochemical materials, with a focus on charge-transfer fundamentals.
Relevance: Core · 11483 · 1. Introduction
Compares contactless mobility probes, two-probe, four-probe, van der Pauw, bandgap, activation energy, and band-structure analyses.
Relevance: Core · 11488 · 4. Measurement Technique · Figures 6-9
Identifies unresolved issues: incomplete mechanism understanding, sparse mobility data, missing measurement conditions, underestimated out-of-plane transport, and stability gaps.
Relevance: Core · 11533 · 12. Summary and Outlook
Discusses mixed-metal, mixed-ligand, and metal-based hopping as distinct from extended-conjugation band transport.
Relevance: Core · 11514 · 8. Redox Hopping
Positions spectroelectrochemistry as a way to link charge-transfer processes, oxidation states, electronic transitions, and conductive MOF mechanisms.
Relevance: Supporting · 11521 · 10. Spectroelectrochemistry · Figure 39
Reviews MOF-74, azolate, and other through-bond families where metal-linker orbital matching and redox matching support charge transport.
Relevance: Core · 11490 · 5. Through Bond Pathway · Figure 11
Covers TTF and other aromatic pi-stacked frameworks where non-covalent orbital overlap provides charge-transport pathways.
Relevance: Core · 11511 · 7. Through-Space Mechanism · Figure 26
Defines conductivity, carrier density, mobility, hopping, VRH, band theory, effective mass, and Marcus-style redox hopping concepts for MOFs.
Relevance: Core · 11484 · 2. Electrical Conductivity and Charge Transfer Mechanism
Classification systems are attributed to this review and are not treated as a global material registry.
The review uses applications to show why electronic conductivity, porosity, and active-site density must be treated together.
Categories: Electrochemical capacitors · Li-ion, Na-ion, Zn, and Li-S batteries · ORR, OER, and HER electrocatalysis · Electrochemical sensors
11483 · 1. Introduction
The review uses these categories to organise the main routes by which insulating porous MOFs are converted into conductive frameworks.
Categories: Through-bond orbital overlap · Through-space pi-pi interactions · Guest incorporation · Chemical engineering and post-synthetic modification
11483 · 1. Introduction
The review subdivides high-conductivity extended-conjugation MOFs by linker chemistry and coordination motif.
Categories: Tetraoxolene/dhbq · Semiquinoid HHTP/HHB/THQ · Thiolate THT/BHT · Imino HITP/HIB · Selenol TPHS/BHSe
11499 · 6. Extended Conjugation · Figure 15
Guest incorporation is treated as an extrinsic route where host-guest orbital alignment, redox potential, and pore topology determine conductivity changes.
Categories: Iodine and polyiodide · Organic and metallocarbene infiltration · Polymer incorporation · Oxide incorporation
11517 · 9. Guest Incorporated Conductivity
The review distinguishes contactless and contact methods, then cautions that contact resistance, grain boundaries, and anisotropy affect interpretation.
Categories: TRTS · FP-TRMC · Hall measurement · FET · Two-probe · Four-probe · Van der Pauw
11488 · 4. Measurement Technique · Figures 6-8
The review separates physical transport concepts from chemical design language, linking hopping/band models to through-bond and through-space MOF design.
Categories: Redox hopping · Band transport in extended delocalized pi-conjugated systems · Through-bond pathways · Through-space pathways
11483 · 1. Introduction
Review-defined families retain their representative materials and conduction descriptions.
Frameworks using redox-active tetraoxolene/dihydroxybenzoquinone linkers to tune ligand oxidation states and mixed-valence transport.
Conduction: Conductivity is tied to mixed-valence ligand states, electron/hole doping, and activation-energy changes after redox modification.
Representative materials: (NBu4)2Fe2(dhbq)3 · (Me2NH2)2[Fe2(Cl2dhbq)3] · reduced Fe-Cl2dhbq MOFs
Nodes / linkers: Fe · Mn · Zn · dhbq · Cl2dhbq
11499 · 6.1. dhbq linker-based MOFs · Figure 14
Azolate-linked Fe frameworks containing integrated Fe-N-N-Fe chains and accessible Fe(II)/Fe(III) mixed-valence states.
Conduction: The review attributes higher conductivity to Fe spin/valence accessibility, short Fe-Fe distances, and polaronic hopping.
Representative materials: Fe(1,2,3-triazolate)2 · Fe2(BDT)3 · Fe2(BDP)3
Nodes / linkers: Fe · 1,2,3-triazolate · BTDD · BDT · BDP
11491 · 5.2. Azolate MOFs · Figure 13
Porous frameworks whose conductivity is increased or altered by guests such as iodine, TCNQ, C60, conductive polymers, or metal oxides.
Conduction: Conductivity depends on guest-host orbital alignment, dopant redox chemistry, guest size, and whether a continuous transport path forms.
Representative materials: Cu3(BTC)2@TCNQ · NU-901@C60 · PPy@MOF · NU-1000-Sn-SIM
Nodes / linkers: Cu · Zn · Cd · Zr · Cr · BTC · porphyrin · NDC · NU-1000 linkers
11517 · 9. Guest Incorporated Conductivity · Figures 34-38
2D honeycomb catecholate frameworks based on HHTP and related semiquinoid linkers.
Conduction: In-plane and out-of-plane conductivities can be comparable in order of magnitude, challenging a purely in-plane transport assumption.
Representative materials: Cu3(HHTP)2 · Ni3(HHTP)2 · Co3(HHTP)2
Nodes / linkers: Cu · Ni · Co · Fe · HHTP · catecholate · semiquinoid
11503 · 6.3.1. Hexahydroxytriphenylene-MOFs · Figure 18
2D imine/iminosemiquinone conjugated frameworks built from hexaiminotriphenylene or hexaaminobenzene-derived ligands.
Conduction: High conductivities arise from extended pi conjugation, metal-ligand electronic coupling, and in some cases high crystallinity or hollow-sphere morphologies.
Representative materials: Ni3(HITP)2 · Cu3(HIB)2 · Ni3(HIB)2 · Mn/Fe-HIB-MOF
Nodes / linkers: Ni · Cu · Co · Mn · Fe · HITP · HIB · HAB
11509 · 6.5. Imino ligand-based MOFs · Figure 24
Frameworks in which distinct ligand units, often photochromic or redox-active, act as switchable wires or hopping sites.
Conduction: Photoisomerisation and ligand conformation alter bandgap, spatial separation, and hopping rates.
Representative materials: Zn2(BPDC)2(BPMTC) · Zn2(SDC)2(BPMTC) · Zr6O4(OH)8(Me2BPDC)4
Nodes / linkers: Zn · Zr · diarylethene · spiropyran · BPDC · BPMTC
11515 · 8.2. Mixed-ligands hopping · Figure 31
Porous M2(DOBDC) or related M2(DSBDC) frameworks with 1D hexagonal channels and infinite metal-oxo or metal-thiolate chains.
Conduction: Conductivity is interpreted through redox/orbital matching, metal identity, guest coordination, and hopping along metal-oxo or metal-sulfur chains.
Representative materials: Mn2(DSBDC)(DMF)2 · Fe2(DSBDC)(DMF)2 · ANMOF-74(M)
Nodes / linkers: Mn · Fe · Zn · Mg · Co · Ni · DOBDC · DSBDC · anthracene-modified MOF-74 linkers
11490 · 5.1. MOF-74-type · Figure 12
2D thiolate-linked frameworks using triphenylenehexathiolate, benzenehexathiol, or related sulfur-rich linkers.
Conduction: Sulfur substitution improves orbital overlap; some examples are described as metallic or band-like, while defects and guest species complicate interpretation.
Representative materials: Fe3(THT)2(NH4)3 · Co-THT · Cu3(BHT) · Ni-BHT
Nodes / linkers: Fe · Co · Cu · Ni · Ag · Pd · THT · BHT · dithiolene
11506 · 6.4. Thiolate ligands-based MOFs
Frameworks containing tetrathiafulvalene-derived linkers where close stacking and radical-cation states support through-space charge transfer.
Conduction: Conductivity is linked to TTF stacking distance, oxidation state, radical-cation concentration, and S-S contacts.
Representative materials: Zn2TTFTB · Cd2TTFTB · MUV-5 TTFTB
Nodes / linkers: Zn · Cd · Mn · Co · lanthanides · TTFTB · TTF(py)4
11511 · 7.1. Tetrathiafulvalene (TTF) based frameworks · Figure 26
Review-level synthesis principles remain separate from primary-study recipes.
Build planar layered frameworks from redox-active linkers and square-planar metal nodes to extend conjugation in and across layers.
Claimed effects: Produces many of the highest reported conductive MOFs and enables in-plane/out-of-plane transport comparisons.
Controlling variables: Linker symmetry · Stacking mode · Metal coordination geometry · Grain size and crystallinity
Representative materials: Cu3(HHTP)2 · Ni3(HITP)2 · Cu3(BHT)
Caveat: Polycrystalline films and pellets can understate intrinsic conductivity and hide anisotropy.
11499 · 6. Extended Conjugation
Introduce iodine, TCNQ, C60, viologen, or related guests into MOF pores to create donor-acceptor stacks or charge-transfer complexes.
Claimed effects: Can raise conductivity by orders of magnitude and lower effective bandgaps, but may reflect extrinsic guest pathways.
Controlling variables: Guest redox potential · Guest size · Pore topology · Host-guest orbital alignment · Guest loading
Representative materials: Cu3(BTC)2@TCNQ · NU-901@C60 · iodine-doped pybz MOFs
Caveat: Conductivity may be limited by guest orientation, incomplete continuous pathways, or framework degradation.
11517 · 9. Guest Incorporated Conductivity
Integrate spiropyran or diarylethene linker wires so light-induced isomerisation changes bandgap and hopping rate.
Claimed effects: The review reports modest but mechanistically useful conductivity increases after irradiation.
Controlling variables: Photoisomerisation state · Frontier-orbital delocalisation · Linker spacing · Framework rigidity
Representative materials: Zn2(BPDC)2(BPMTC) · Zn2(SDC)2(BPMTC) · Zr6O4(OH)8(Me2BPDC)4
Caveat: Reported enhancements are small relative to top intrinsic conductors and depend on reversible photochemistry.
11515 · 8.2. Mixed-ligands hopping · Figure 31
Use MOF pores as templates for conductive polymers or inorganic oxide wires to create hybrid conductive pathways.
Claimed effects: Can raise conductivity by several orders of magnitude while retaining aspects of MOF porosity or morphology.
Controlling variables: Pore aperture · Polymerisation method · Oxide loading cycles · Host stability · Directional confinement
Representative materials: PPy@MOF · ppy-S-in-MIL-101 · NU-1000-Sn-SIM
Caveat: The conductive phase may dominate the transport interpretation and obscure intrinsic framework conduction.
11520 · 9.3. Polymer and oxide incorporation · Figure 38
Select metals and conjugated linkers with compatible orbital symmetry and redox energies to promote through-bond charge transport.
Claimed effects: Improves charge delocalisation and can lower activation barriers relative to orbital-mismatched analogues.
Controlling variables: Metal d-orbital energy · Linker donor atom hardness or softness · Metal-linker covalency · Redox potential matching
Representative materials: Mn2(DSBDC)(DMF)2 · Fe2(DSBDC)(DMF)2 · Fe-azolate MOFs
Caveat: Flat bands, localized orbitals, and grain boundaries can still make hopping dominant even when orbital matching improves conductivity.
11490 · 5. Through Bond Pathway · Figure 11
Grow larger or oriented crystals and fabricate directional devices to separate intrinsic conductivity from grain-boundary effects.
Claimed effects: Allows anisotropic in-plane and out-of-plane conductivities to be measured more directly.
Controlling variables: Growth direction · Substrate · Reaction time · Solvent proportion · Metal precursor-linker separation
Representative materials: Cu3(HHTP)2 · Ni-HHTP
Caveat: The review says single-crystal devices require small-crystal handling skill and are absent from much of the literature.
11504 · 6.3.1. Hexahydroxytriphenylene-MOFs
Replace harder O donors with softer S donors to reduce orbital mismatch and enhance metal-linker electronic coupling.
Claimed effects: The review reports higher conductivity for sulfur-containing analogues relative to oxygen analogues in selected MOF-74 derivatives.
Controlling variables: Donor atom identity · Metal centre · Metal-ligand bond covalency · Framework isostructurality
Representative materials: Mn2(DOBDC)(DMF)2 · Mn2(DSBDC)(DMF)2 · Fe2(DSBDC)(DMF)2
Caveat: The review notes that hopping remains likely and that guest removal can introduce defects and grain boundaries.
11491 · 5.1. MOF-74-type
Use metal centres such as Fe that can support accessible spin and valence states to create localized charge density and polaronic hopping.
Claimed effects: Explains why Fe analogues can outperform isostructural closed-shell or less redox-active congeners.
Controlling variables: Fe(II)/Fe(III) ratio · Spin state · Metal-metal distance · Air or iodine oxidation
Representative materials: Fe(1,2,3-triazolate)2 · Fe2(BDT)3 · KxFe2(BDP)3
Caveat: Small fractions of Fe(III) may be hard to detect without EPR or Mossbauer analysis.
11492 · 5.2. Azolate MOFs · Figure 13
Use electron-rich organic donors such as TTF to create close intermolecular stacks and radical cation pathways.
Claimed effects: Can generate anisotropic single-crystal conduction through non-covalent orbital overlap.
Controlling variables: Stacking distance · S-S contact · Cation size · Oxidation state · Framework topology
Representative materials: Zn2TTFTB · Cd2TTFTB · MUV-5 TTFTB
Caveat: Some polymorphs conduct poorly when frontier-orbital overlap between adjacent molecules is weak.
11512 · 7.1. Tetrathiafulvalene (TTF) based frameworks
These are the review authors’ synthesis, not newly measured results.
Conductivity must be interpreted through both charge-carrier density and mobility; conductivity alone does not fully describe electronic transport.
Evidence basis: review_reasoning
Caveat: The review itself notes that mobility is rarely reported for conductive MOFs.
11484 · 2. Electrical Conductivity and Charge Transfer Mechanism · Equation 1
Conductive MOFs can act as electrode materials without conductive additives in selected energy-storage demonstrations, linking intrinsic conductivity to device simplification.
Evidence basis: multi_reference
Caveat: The review also states commercialisation remains distant and stability needs more scrutiny.
11522 · 11.1.1. Electrochemical capacitors
For electrocatalysis, conductive MOFs are attractive because they combine electronic conductivity, high active-site density, porosity, and tunable morphologies.
Evidence basis: multi_reference
Caveat: The review is application-facing here; primary device data should be checked in the cited papers.
11527 · 11.2. Electrocatalyst
The review treats extended-conjugation frameworks as the major source of high-conductivity MOFs, especially 2D pi-conjugated families.
Evidence basis: multi_reference
Caveat: Reported values remain sensitive to crystallinity, film morphology, and method.
11499 · 6. Extended Conjugation
The review interprets Fe-based MOFs as unusually conductive among several isostructural families because Fe spin and mixed-valence states contribute to valence-band character and hopping.
Evidence basis: multi_reference
Caveat: The Fe(III) fraction can be very small and requires sensitive characterisation.
11492 · 5.2. Azolate MOFs · Figure 13
Polycrystalline pellets and films often underestimate intrinsic conductivity and obscure anisotropic transport because of grain boundaries and random crystallite orientation.
Evidence basis: review_reasoning
Caveat: Single-crystal devices are preferred but practically difficult.
11488 · 4.2. Electrical conductivity measurement
Guest incorporation can greatly increase MOF conductivity, but those values must be interpreted as host-guest or guest-derived transport rather than intrinsic framework conductivity.
Evidence basis: multi_reference
Caveat: This extraction treats such benchmarks as extrinsic secondary context.
11517 · 9. Guest Incorporated Conductivity
In MOF-74-type Fe2(DSBDC), guest coordination is interpreted as changing charge density rather than mobility, and non-interacting guests do not reproduce the conductivity effect.
Evidence basis: single_reference
Caveat: This is a review interpretation of a specific MOF-74-type case.
11491 · 5.1. MOF-74-type
The review identifies missing measurement temperature, environmental conditions, mobility, and complete conductivity databases as major literature limitations.
Evidence basis: review_reasoning
Caveat: This is a secondary synthesis gap, not a measured result.
11533 · 12. Summary and Outlook
MOFs were originally pursued for porosity-centred functions, but conductive MOFs have emerged as a recent route to electronic and electrochemical materials.
Evidence basis: multi_reference
Caveat: The review frames this as field evolution, not as a single discovery claim.
11483 · 1. Introduction
The review argues that out-of-plane transport in 2D conductive MOFs has often been underestimated and can contribute comparably to in-plane transport.
Evidence basis: multi_reference
Caveat: This point depends on high-quality single-crystal or direction-specific measurements that are still sparse.
11504 · 6.3.1. Hexahydroxytriphenylene-MOFs
Spectroelectrochemistry is presented as a bridge between electrochemical modulation and mechanistic assignment of charge-transfer species.
Evidence basis: multi_reference
Caveat: The review gives examples rather than a standardised protocol for all MOF systems.
11521 · 10. Spectroelectrochemistry
Thiolate-based MOFs can show metallic-like behaviour, but defects, guest species, and structural changes complicate a clean intrinsic-conductivity assignment.
Evidence basis: multi_reference
Caveat: The review explicitly calls for greater insight into electronic structure for these systems.
11507 · 6.4. Thiolate ligands-based MOFs
Through-bond conduction requires redox matching plus orbital symmetry and energy overlap between metal nodes and conjugated linkers.
Evidence basis: multi_reference
Caveat: Good matching does not guarantee band-like transport; many examples remain hopping dominated.
11490 · 5. Through Bond Pathway · Figure 11
Through-space conduction is governed by pi-stack geometry, S-S contacts, radical-cation content, and cation-controlled framework contraction.
Evidence basis: multi_reference
Caveat: The same family can show orders-of-magnitude variation when stacking motifs change.
11512 · 7.1. Tetrathiafulvalene (TTF) based frameworks
Two-probe values can be degraded by contact resistance, while four-probe and van der Pauw methods mitigate different measurement artefacts.
Evidence basis: review_reasoning
Caveat: Van der Pauw gives an average value and may miss direction-specific conductivity.
11488 · 4.2. Electrical conductivity measurement · Figures 6-8
VRH/hopping models are widely used for disordered or grain-boundary-dominated conductive MOFs, but extended conjugation can make band-theory descriptions more appropriate.
Evidence basis: multi_reference
Caveat: The review notes that some authors questioned VRH validity for conducting organic materials.
11485 · 2. Electrical Conductivity and Charge Transfer Mechanism
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 |
|---|---|---|---|---|---|
| SecondaryCu3(BHT) | Electrical conductivity | 1580 S/cm | Four-probe, film, 300 K; Ea 0.002 eV Table · Exact Reported | research_0006 | 11495 · Table 1 · Table 1, Thiolate ligand-based MOFs |
| SecondaryCu3(BTC)2@TCNQ | Electrical conductivity | 0.07 S/cm | Film; guest-infiltrated Cu3(BTC)2 Table · Exact Reported | research_0088 | 11498 · Table 1 · Table 1, Organic and Metallocarbene infiltration |
| SecondaryCu-HHTP / Cu3(HHTP)2 | Directional electrical conductivity | out-of-plane 1.5 S/cm; in-plane 0.5 S/cm | Four-probe, single crystal, room temperature Table · Exact Reported | research_0005 | 11494 · Table 1 · Table 1, Semiquinoid ligand-based MOFs |
| SecondaryCu-HHTP / Cu3(HHTP)2 | Electrical conductivity | 0.2 S/cm | Four-probe, single crystal, room temperature Table · Exact Reported | No verified corpus mapping | 11494 · Table 1 · Table 1, Semiquinoid ligand-based MOFs |
| SecondaryCu-THQ MOF | Li-ion battery reversible capacity | 387 mAh g^-1 and 775 Wh kg^-1 | Li-ion battery electrode; high specific energy density over 100 cycles Text · Exact Reported | No verified corpus mapping | 11524 · 11.1.2.1. Li-ion battery · Figure 42 |
| Secondary(NBu4)2-Fe2(dhbq)3 | Electrical conductivity | 0.16 S/cm | Two-probe, pellet, 298 K; Ea 0.11 eV Table · Exact Reported | research_0186 | 11493 · Table 1 · Table 1, Extended conjugation |
| SecondaryFe2(BDT)3 (oxidised) | Electrical conductivity | 1.2 S/cm | Two-probe, single crystal, 296 K Table · Exact Reported | No verified corpus mapping | 11493 · Table 1 · Table 1, Azolate MOFs |
| SecondaryFe3(THT)2(NH4)3 | Mobility and conductivity | sigma 3.4 x 10^-2 S/cm; mobility 211 +/- 7 cm2 V^-1 s^-1 (TRTS), 229 +/- 33 cm2 V^-1 s^-1 (Hall) | Four-probe film, 300 K; TRTS and Hall mobility Table · Exact Reported | research_0001 | 11495 · Table 1 · Table 1, Thiolate ligand-based MOFs |
| SecondaryFe2(DSBDC)(DMF)2 | Electrical conductivity | 1.5 x 10^-9 S/cm | Activated, pressed pellet, two-probe, 297 K Table · Exact Reported | No verified corpus mapping | 11493 · Table 1 · Table 1, MOF-74-type |
| SecondaryFe2(DSBDC)(DMF)2 | Electrical conductivity | 3.9 x 10^-6 S/cm | Solvated, pressed pellet, two-probe, 297 K Table · Exact Reported | research_0063 | 11493 · Table 1 · Table 1, MOF-74-type |
| SecondaryFe(1,2,3-triazolate)2 (oxidised, I2) | Electrical conductivity | 1.1 x 10^-3 S/cm | Iodine oxidised, four-probe, pellet Table · Exact Reported | research_0325 | 11493 · Table 1 · Table 1, Azolate MOFs |
| SecondaryFe(1,2,3-triazolate)2 | Electrical conductivity | 7.7 x 10^-5 S/cm | Four-probe, pellet Table · Exact Reported | research_0325 | 11493 · Table 1 · Table 1, Azolate MOFs |
| SecondaryK0.98Fe2(BDP)3 | Electrical conductivity | 0.025 S/cm | Two-probe, single crystal Table · Exact Reported | No verified corpus mapping | 11493 · Table 1 · Table 1, Azolate MOFs |
| SecondaryMn2(DSBDC)(DMF)2 | Electrical conductivity | 2.5 x 10^-12 S/cm | Solvated, pressed pellet, two-probe, 297 K Table · Exact Reported | research_0011 | 11493 · Table 1 · Table 1, MOF-74-type |
| SecondaryNi-HHTP | Directional electrical conductivity | in-plane 2 S/cm; out-plane 1 x 10^-4 S/cm | Single crystal, room temperature; in-plane four-probe and out-plane two-probe Table · Exact Reported | research_0053 | 11494 · Table 1 · Table 1, Semiquinoid ligand-based MOFs |
| SecondaryNi3(HITP)2 | EDLC areal capacitance | 18 microF cm^-2 | EDLC electrode without conductive additive Text · Exact Reported | No verified corpus mapping | 11522 · 11.1.1. Electrochemical capacitors |
| SecondaryNi3(HITP)2 | Electrical conductivity | 150 S/cm | Four-probe, single crystal Table · Exact Reported | research_0005 | 11495 · Table 1 · Table 1, Imino ligand-based MOFs |
| SecondaryNU-901@C60 | Electrical conductivity | 10^-3 S/cm | Two-probe, pellet, room temperature Table · Exact Reported | No verified corpus mapping | 11498 · Table 1 · Table 1, Organic and Metallocarbene infiltration |
| SecondaryZn2(BPDC)2(BPMTC) | Photo-modulated electrical conductivity | 6.4 x 10^-7 S/cm to 1.7 x 10^-6 S/cm after irradiation | Two-probe, pellet, room temperature; before and after irradiation Table · Exact Reported | No verified corpus mapping | 11496 · Table 1 · Table 1, Mixed-ligands Hopping MOFs |
| Secondaryppy-S-in-MIL-101 | Electrical conductivity | 3.11 x 10^1 S/cm | Two-probe; sulfur and polypyrrole incorporated MIL-101 Table · Exact Reported | No verified corpus mapping | 11498 · Table 1 · Table 1, Polymer and oxide incorporation |
| SecondaryZn2TTFTB | Directional electrical conductivity | in-plane 3.95 x 10^-6 S/cm; perpendicular 2.03 x 10^-7 S/cm | Two-probe, single crystal Table · Exact Reported | research_0353 | 11495 · Table 1 · Table 1, Through-space MOFs |
Open questions are presented as review-author priorities, not conclusions from the primary database.
The review states that charge-transfer mechanisms in conductive MOFs remain insufficiently explored.
Proposed direction: Pair rigorous experiments with theoretical calculations and spectroelectrochemical characterisation.
11533 · 12. Summary and Outlook
Conductive MOFs show electrochemical promise but remain far from extensive commercialisation.
Proposed direction: Prioritise cost-effective large-scale synthesis and robust structure-performance relationships.
11533 · 12. Summary and Outlook
The review calls for a more complete database of conductive MOFs.
Proposed direction: Use curated secondary benchmarks only as context, and maintain primary-paper provenance for actual comparative datasets.
11533 · 12. Summary and Outlook
Conductivity reports often omit temperature and environmental conditions, limiting comparisons.
Proposed direction: Standardise reporting of measurement temperature, atmosphere, light exposure, sample form, and contact geometry.
11533 · 12. Summary and Outlook
Only a small number of reported conductive MOFs include mobility values despite mobility being an intrinsic electronic property.
Proposed direction: Report mobility alongside conductivity using Hall, FET, TRTS, FP-TRMC, or comparable methods where possible.
11533 · 12. Summary and Outlook
Out-of-plane conductivity in 2D conductive MOFs is often underestimated or ignored.
Proposed direction: Develop oriented single-crystal and directional film devices that resolve in-plane and out-of-plane contributions.
11533 · 12. Summary and Outlook
Single-crystal measurements are more informative but are limited by small crystal size and fabrication difficulty.
Proposed direction: Improve single-crystal growth and lithographic/contact strategies for direction-specific conductivity.
11488 · 4.2. Electrical conductivity measurement
Structural stability under acidic, basic, or electrochemical conditions is often overlooked despite being crucial for applications.
Proposed direction: Scrutinise framework stability before harsh-condition application testing.
11533 · 12. Summary and Outlook
Mappings show which printed review references have a verified counterpart in the frozen primary corpus.
| Reference | Study | Role and context | Corpus mapping |
|---|---|---|---|
| Ref. 11999 | Title unavailable | historical_framingUsed by the review as background for classical MOF porosity and early framework development. | Unmapped |
| Ref. 32016 | Title unavailable | review_contextReferenced for earlier reviews of applications, fabrication, and conductive MOF context. | Unmapped |
| Ref. 92019 | Title unavailable | through_space · polymorphismUsed for TTFTB polymorphs and the relationship between stacking and conductivity. | Unmapped |
| Ref. 112011 | Title unavailable | transport_theoryCited for critique of VRH use and alternative band-theory interpretation. | Unmapped |
| Ref. 121969 | Title unavailable | transport_theory · VRHCited for Mott variable-range hopping description. | Unmapped |
| Ref. 132005 | Title unavailable | band_theoryCited for Bloch functions and band-theory concepts applied to MOFs. | Unmapped |
| Ref. 20a2018 | Title unavailable | mobility_benchmark · thiolate_mofUsed for terahertz and Hall mobility benchmark in a thiolate conductive MOF. | research_0001 |
| Ref. 272017 | Title unavailable | fe_uniqueness · transport_mechanismCentral theoretical/experimental comparison for why Fe analogues show high conductivities. | research_0221 |
| Ref. 282013 | Title unavailable | mof74 · conductivity_benchmarkUsed for sulfur-substituted MOF-74-type framework, mobility, and delocalisation discussion. | research_0011 |
| Ref. 292015 | Title unavailable | mof74 · conductivity_benchmarkUsed for Fe substitution in MOF-74 analogues and conductivity increases relative to Mn analogues. | research_0063 |
| Ref. 302018 | Title unavailable | guest_coordination · mof74Used for the effect of DMF coordination on activated Fe2(DSBDC) conductivity. | Unmapped |
| Ref. 412012 | Title unavailable | azolate · conductivity_benchmarkUsed for isostructural metal-triazolate MOFs and iodine-induced conductivity increase in Fe triazolate. | research_0325 |
| Ref. 422018 | Title unavailable | azolate · single_crystalUsed for metal mixed-valency effects on conductivity in a tetrazole-based MOF. | Unmapped |
| Ref. 43b2018 | Title unavailable | azolate · redox_insertionUsed for reductive insertion in Fe2(BDP)3 and mobility enhancement along single-crystal chains. | Unmapped |
| Ref. 482015 | Title unavailable | dhbq · extended_conjugationUsed for early 3D mixed-valence tetraoxolene framework conductivity. | research_0186 |
| Ref. 602012 | Title unavailable | hhtp · 2d_conjugated_mofPioneering HHTP/catecholate 2D MOF family cited as the start of extended conjugated 2D MOFs. | Unmapped |
| Ref. 682019 | Title unavailable | anisotropy · single_crystalUsed for single-crystal and morphology-based in-plane/out-of-plane transport comparisons in 2D conductive MOFs. | research_0005 |
| Ref. 692021 | Title unavailable | single_crystal_growth · anisotropyUsed for biphasic solution-solid growth of in-plane Ni-HHTP crystals and directional conductivity measurements. | research_0053 |
| Ref. 702020 | Title unavailable | out_of_plane_transport · lanthanide_hhtpUsed for lanthanide HHTP frameworks with significant out-of-plane electronic communication. | research_0047 |
| Ref. 72c2014 | Title unavailable | hitp · conductivity_benchmarkOriginal Ni3(HITP)2 benchmark cited in Table 1 and the imino ligand discussion. | Unmapped |
| Ref. 762014 | Title unavailable | bht · thin_filmUsed for nickel bis(dithiolene) nanosheet conductivities and oxidation-state tuning. | research_0361 |
| Ref. 842017 | Title unavailable | thiolate · electrocatalysisUsed for Co-THT conductivity and HER-related application context. | Unmapped |
| Ref. 862018 | Title unavailable | bht · high_conductivityUsed for crystalline Cu-BHT nanosheet and very high conductivity/metallicity claims. | Unmapped |
| Ref. 912015 | Title unavailable | bht · conductivity_benchmarkUsed in Table 1 for high Cu3(BHT) film conductivity and mobility values. | research_0006 |
| Ref. 95a2017 | Title unavailable | energy_storage · hitpUsed for conductive Ni3(HITP)2 as EDLC electrode without conductive additive. | Unmapped |
| Ref. 1202015 | Title unavailable | through_space · ttfUsed for TTF-based through-space MOFs and single-crystal anisotropic conductivity. | research_0353 |
| Ref. 1212016 | Title unavailable | through_space · measurement_comparisonUsed for different techniques and environmental effects in Cd2TTFTB conductivity measurements. | research_0010 |
| Ref. 1482019 | Title unavailable | photoresponsive · mixed_ligand_hoppingUsed for diarylethene/spiropyran-linked photoresponsive conductivity changes. | Unmapped |
| Ref. 1632010 | Title unavailable | iodine_guest · anisotropyUsed for iodine-infiltrated porous MOF with single-crystal-to-single-crystal modification and anisotropic conductivity. | Unmapped |
| Ref. 1762014 | Title unavailable | guest_infiltration · tcnqCanonical TCNQ infiltration example used for large conductivity increase in HKUST-1. | research_0088 |
| Ref. 1882018 | Title unavailable | fullerene_guest · conductivity_benchmarkUsed for fullerene incorporation in NU-901 and conductivity enhancement while maintaining porosity. | Unmapped |
| Ref. 1952018 | Title unavailable | polymer_incorporation · hybrid_conductivityUsed for sulfur and polypyrrole incorporation into MOFs and large conductivity increases. | Unmapped |
| Ref. 197a2018 | Title unavailable | oxide_incorporation · nu1000Used for solvo-thermal installation of conductive tin oxide arrays inside NU-1000. | research_0106 |
| Ref. 1982009 | Title unavailable | spectroelectrochemistryCited for spectroelectrochemical concepts used to probe charge transfer. | Unmapped |
| Ref. 2022018 | Title unavailable | spectroelectrochemistry · through_space_ivctUsed for solid-state spectroelectrochemical demonstration of through-space IVCT. | Unmapped |
| Ref. 2092018 | Title unavailable | li_ion_battery · hitpUsed for Ni-HIB as MOF-based cathode material for Li-ion batteries. | Unmapped |
| Ref. 2102020 | Title unavailable | li_ion_battery · cu_thqUsed for comprehensive Li-ion insertion mechanism in conductive Cu-THQ MOF. | Unmapped |
| Ref. 2232016 | Title unavailable | orr · ni3_hitpUsed for intrinsic electrically conductive Ni3(HITP)2 as an ORR electrocatalyst. | research_0003 |
| Ref. 2302020 | Title unavailable | orr_oer · semiconductive_mofUsed for bifunctional ORR/OER activity in a semiconductive MOF. | Unmapped |
| Ref. 2462020 | Title unavailable | her · hahhatnUsed for bidentate Ni-Ni motif and HER activity in conductive HAHATN MOFs. | research_0513 |