Kangmin Lee, Jumin Park, Intek Song et al. · Bulletin of the Korean Chemical Society · 2021
To introduce recent research achievements in MOF spintronics alongside conductive MOF development, basic magnetism, design rules for MOF magnets, and practical spintronic outlooks.
The review’s argument is preserved as a navigable set of section summaries.
Reviews theoretical 2D MOF spin-filter predictions and experimental examples of high-temperature magnetic/conductive 2D MOFs and Cu3(HHTP)2 organic spin valves.
Relevance: Core · 1176 · 2D MOFs Films for Spintronics
Summarises why MOFs are attractive for spintronics and lists needs for defect-controlled films, single-crystal transport understanding, room-temperature operation and stability.
Relevance: Core · 1178 · Conclusion
Uses GKA rules to connect metal-ligand-metal angles, orbital occupancy and exchange pathways to MOF ferro- or antiferromagnetism.
Relevance: Core · 1174 · Goodenough-Kanamori-Anderson Rule
Frames spintronics, GMR/TMR spin-valve operation, organic/inorganic spin-transport limitations, and why conductive MOFs are plausible hybrid spintronic materials.
Relevance: Core · 1171 · Introduction
Defines magnetic moment, magnetisation, susceptibility, ferro-/antiferromagnetism, hysteresis, domains, and Curie-Weiss interpretation for reading MOF magnetism claims.
Relevance: Supporting · 1172 · Basic Principles of Magnetism for Designing MOF Magnets
Classification systems are attributed to this review and are not treated as a global material registry.
The review moves from calculated Kagome and superlattice spin filters to K3Fe2[PcFe-O8] and Cu3(HHTP)2 experiments, then to fabrication and stability gaps.
Categories: first-principles predictions · conductive/magnetic material demonstrations · spin-valve device demonstrations · outlook challenges
1176 · 2D MOFs Films for Spintronics
GKA treatment provides an orbital-level taxonomy for predicting magnetic ordering in MOFs, especially where metal-ligand-metal angles and electronic configurations are known.
Categories: half-filled/half-filled gives AFM · half-filled/empty gives FM · filled/half-filled gives FM · net exchange from competing pathways
1174 · Goodenough-Kanamori-Anderson Rule
The review distinguishes positive and negative susceptibility classes, long-range ordered FM/AFM states, hysteretic behaviour, and ferrimagnetic uncompensated sublattices.
Categories: diamagnetism · paramagnetism · ferromagnetism · antiferromagnetism · ferrimagnetism
1172 · Magnetic Moments and Magnetic Fields in Condensed Matter
The account separates MOFs that supply FM/AFM magnetic order from conductive 2D MOFs used as active or spacer layers in spin valves and spin filters.
Categories: magnetic electrode · non-magnetic spacer · active spin-filter layer · organic spin-valve semiconductor
1172 · Introduction
The review organises spintronic operation around FM/NM/FM sandwiches where parallel alignment lowers resistance, antiparallel alignment raises it, and thin spacers enable tunnelling magnetoresistance.
Categories: GMR · TMR · parallel FM alignment · antiparallel FM alignment
1171 · Introduction
Review-defined families retain their representative materials and conduction descriptions.
Layered MOFs with transition metals coordinated by N, O, or S donors in triphenylene, ortho-disubstituted benzene or coronene-like ligands.
Conduction: The review states conductivities have developed up to 10^5 S/m for this broad family, while selected spintronic examples are semiconducting.
Representative materials: Cu3(HHTP)2 · K3Fe2[PcFe-O8] · M3C12X12
Nodes / linkers: Cu · Fe · Re · Os · Ta · W · triphenylene · phthalocyanine · Kagome C12X12 ligands · dithioline
1172 · Introduction
Conductive 2D MOF thin film used between LSMO and Co ferromagnetic electrodes in an organic spin valve.
Conduction: Semiconducting Cu3(HHTP)2 thin films support inverse magnetoresistance in a vertical sandwich device.
Representative materials: Cu3(HHTP)2 · LSMO/Cu3(HHTP)2/Co
Nodes / linkers: Cu · HHTP · hexahydroxytriphenylene
1178 · 2D MOFs Films for Spintronics
Semiconducting layered 2D MOF with iron phthalocyanine cores and iron-bis(dihydroxy) ligand coordination.
Conduction: p-type semiconducting behaviour, high mobility and observable magnetoresistance up to room temperature are reported secondarily.
Representative materials: K3Fe2[PcFe-O8]
Nodes / linkers: Fe · phthalocyanine · octahydroxy phthalocyaninato ligands
1177 · 2D MOFs Films for Spintronics
Theoretically evaluated 2D Kagome MOFs with 5d transition metals and O, S or NH ligand groups.
Conduction: Predicted bipolar magnetic semiconductor and half-metallic behaviour relevant to spin-filter devices.
Representative materials: Re3C12N12H12 · Re3C12O12 · M3C12X12
Nodes / linkers: Ta · W · Re · Os · C12O12 · C12S12 · C12N12H12
1176 · 2D MOFs Films for Spintronics
MOFs designed for long-range magnetic order through exchange interactions between metal centres and organic ligands.
Conduction: Magnetism is central; many examples are not presented as highly conductive.
Representative materials: MIL-77 · Co(meso-2,3-dmsucc) · Fe-MOF-74 · MIL-82 · MIL-47as · IFP-5
Nodes / linkers: Co · Mn · Fe · V · short linkers · metalloligands · radical organic linkers · carboxylates
1174 · Goodenough-Kanamori-Anderson Rule
MOFs with pyrazine or dihydroxybenzoquinone-type ligands that couple conductivity with magnetic exchange.
Conduction: Reported conductivities as high as 20 S/m and long-range charge transport.
Representative materials: pyrazine-based MOFs · dihydroxybenzoquinone-based MOFs
Nodes / linkers: transition metals · pyrazine · dihydroxybenzoquinone
1172 · Introduction
Predicted naphthalene-amine and bis(dithioline) 2D MOFs with Cr, Mn, Fe or Co centres.
Conduction: Calculated spin-polarized I-V and near-100% spin-filtering behaviour for selected systems.
Representative materials: Cr naphthalene-coordinated 2D MOF · Fe naphthalene-coordinated 2D MOF · Co-bdt
Nodes / linkers: Cr · Mn · Fe · Co · amine-functionalised naphthalene · bis(dithioline)
1177 · 2D MOFs Films for Spintronics
Review-level synthesis principles remain separate from primary-study recipes.
Use guest adsorption to change local geometry and electronic configuration in a magnetic MOF.
Claimed effects: Can shift magnetic ordering and provide structure-property tests of orbital models.
Controlling variables: guest molecule · coordination geometry · electronic configuration · framework flexibility
Representative materials: Fe(II)-MOF-74
Caveat: Presented as a mechanistic example rather than a mature device strategy.
1176 · Goodenough-Kanamori-Anderson Rule
Deposit multilayer conductive MOF on functionalised LSMO using repeated solvothermal cycles before adding the second FM electrode.
Claimed effects: Creates a tunable MOF spacer for vertical organic spin-valve testing.
Controlling variables: surface functionalisation · number of growth cycles · film thickness · crystallinity · defect density
Representative materials: Cu3(HHTP)2 · LSMO/Cu3(HHTP)2/Co
Caveat: Review stresses that thin-film optimisation and large-area low-defect fabrication remain unresolved.
1178 · 2D MOFs Films for Spintronics
Apply GKA reasoning to select metal centres and bridging geometries that favour the desired net exchange.
Claimed effects: Enables rational FM/AFM assignment and design of MOF magnetic properties.
Controlling variables: M-L-M angle · metal d-electron count · sigma versus pi superexchange · direct exchange
Representative materials: Co(meso-2,3-dmsucc) · Mn(meso-2,3-dmsucc) · Fe-MOF-74 · IFP-5
Caveat: Large-ligand MOFs may require revised or more detailed treatments beyond simple GKA rules.
1174 · Goodenough-Kanamori-Anderson Rule
Coordinate transition metals with conjugated N/O/S donor ligands to create in-plane electronic coupling and magnetic anisotropy.
Claimed effects: Improves electrical conductivity, long-range spin arrangement and high-temperature spin diffusion prospects.
Controlling variables: metal identity · donor atom · ligand conjugation · 2D crystallinity
Representative materials: Cu3(HHTP)2 · K3Fe2[PcFe-O8] · M3C12X12
Caveat: Still difficult to achieve high-temperature ferromagnetism and practical device-quality films.
1178 · Conclusion
Use metalloligands, radical organic linkers and short bridges to reduce the porosity/exchange trade-off in MOF magnets.
Claimed effects: Supports stronger exchange interactions and long-range magnetic order.
Controlling variables: linker length · radical character · metal-ligand-metal geometry · orbital overlap
Representative materials: MOF magnets · MIL-77 · Co(meso-2,3-dmsucc)
Caveat: High porosity can reduce efficient magnetic exchange interactions.
1174 · Goodenough-Kanamori-Anderson Rule
Use metal substitution/transmetallation in fixed 2D lattices to tune magnetoelectronic properties computationally or synthetically.
Claimed effects: Identifies bipolar magnetic semiconductors and spin-filter candidates.
Controlling variables: transition metal · ligand group · spin-polarized band structure · Fermi level
Representative materials: M3C12X12 · Re3C12N12H12 · Re3C12O12
Caveat: This section is mainly theoretical; experimental validation is a remaining need.
1176 · 2D MOFs Films for Spintronics
These are the review authors’ synthesis, not newly measured results.
Conductive conjugated 2D MOFs are highlighted as promising spintronic platforms because they can combine pi-d transport pathways, weak ligand spin-orbit coupling, crystalline long-range ordering and processable thin-film geometries.
Evidence basis: multi_reference
Caveat: The authors state high-temperature ferromagnetism is still challenging.
1176 · 2D MOFs Films for Spintronics
Enhanced MOF charge transport has been achieved through proton or hydroxide transfer, polar metal nodes, conductive additives, redox-active ligands and pi-d conjugation in 2D planes.
Evidence basis: multi_reference
Caveat: The account summarises routes but does not adjudicate which is best for spin transport.
1172 · Introduction
Cu3(HHTP)2 is used as the review's central MOF organic spin-valve example, with inverse magnetoresistance attributed to charge delocalisation and strong p-d coupling from mixed-valent Cu sites.
Evidence basis: single_reference
Caveat: The review reports a strong low-temperature effect that declines sharply with temperature.
1178 · 2D MOFs Films for Spintronics
MOF spintronics is described as early-stage, with film quality, single-crystal charge/spin transport, room-temperature performance and framework stability still limiting practical application.
Evidence basis: review_reasoning
Caveat: This is the review authors' outlook synthesis.
1178 · Conclusion
For MOF magnets, magnetic order is interpreted through exchange interactions governed by orbital occupancy, M-L-M angle, and electronic configuration, making GKA rules a useful but simplified design language.
Evidence basis: multi_reference
Caveat: The review notes that complex larger-ligand structures may require revision of simple GKA arguments.
1174 · Goodenough-Kanamori-Anderson Rule
K3Fe2[PcFe-O8] is presented as a key experimental example where layered 2D MOF magnetisation, semiconducting transport and magnetoresistance persist near room temperature.
Evidence basis: single_reference
Caveat: The benchmark comes from the cited primary study as summarised by the review.
1177 · 2D MOFs Films for Spintronics
MOFs are framed as attractive spintronic materials because structural tunability and chemically designable pores can be combined with improved electrical conductivity and magnetic ordering.
Evidence basis: multi_reference
Caveat: The review repeatedly emphasises infancy and device-processing gaps.
1170 · Abstract
Organic semiconductors offer weaker spin-orbit coupling and longer spin alignment lifetimes than inorganic materials, but low conductivity, limited stability and film-quality control restrict spintronic performance.
Evidence basis: multi_reference
Caveat: The review cites several organic spintronics sources but does not present a single definitive benchmark study for all limitations.
1171 · Introduction
Combining high porosity with strong magnetic ordering is difficult because porosity can reduce efficient exchange interactions.
Evidence basis: review_reasoning
Caveat: General design caveat rather than a quantitative rule.
1174 · Goodenough-Kanamori-Anderson Rule
The review defines the conventional spin-valve measurement architecture as an FM/NM/FM sandwich where resistance changes with parallel or antiparallel spin-polarized transport.
Evidence basis: review_reasoning
Caveat: General spintronics background, not MOF-specific evidence.
1171 · Introduction
The interface between ferromagnetic electrodes and the non-magnetic spacer, described as the spinterface, is treated as a major determinant of spin-valve magnetoresistance magnitude.
Evidence basis: multi_reference
Caveat: The review relies on prior OSV literature for this framing.
1177 · 2D MOFs Films for Spintronics
For 2D MOFs in spintronics, the review says theoretical estimation has often preceded experiment, especially for magnetoelectronic properties and spin-filter concepts.
Evidence basis: multi_reference
Caveat: Calculations are design evidence, not device performance measurements.
1176 · 2D MOFs Films for Spintronics
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 |
|---|---|---|---|---|---|
| SecondaryCo(meso-2,3-dmsucc) | M-L-M angle and magnetic assignment | FM; 86.00 degrees | Table 1 review benchmark Table · Exact Reported | No verified corpus mapping | 1175 · Goodenough-Kanamori-Anderson Rule · Table 1 |
| SecondaryCo-bdt | calculated spin-filtering efficiency | almost 100% SFE | Two-probe spin-polarized charge-transport calculation along z-axis Text · Approximate | No verified corpus mapping | 1178 · 2D MOFs Films for Spintronics |
| SecondaryCu3(HHTP)2 | activation energy | Ea = 0.13 eV | Temperature-dependent electrical conductivity; semiconducting behaviour Text · Exact Reported | research_0129 | 1178 · 2D MOFs Films for Spintronics |
| SecondaryLSMO/Cu3(HHTP)2/Co | inverse magnetoresistance magnitude | around 25% negative MR at 10 K; 3% observed up to 200 K; vanished at 250 K | Vertical organic spin-valve; MR = (RAP - Rp)/Rp x 100% Text · Approximate | research_0129 | 1178 · 2D MOFs Films for Spintronics |
| SecondaryCu3(HHTP)2 | electrical conductivity | 0.29 S cm-1 at 300 K | Four-probe measurement at 300 K Text · Exact Reported | research_0129 | 1178 · 2D MOFs Films for Spintronics |
| SecondaryCu3(HHTP)2 thin film | film thickness tunability | 30 nm to 100 nm | Layer-by-layer solvothermal growth on functionalised LSMO surface Text · Range | research_0129 | 1178 · 2D MOFs Films for Spintronics |
| SecondaryFe-MOF-74 | M-L-M angle and magnetic assignment | FM; 92.0, 89.9 degrees | Table 1 review benchmark Table · Exact Reported | No verified corpus mapping | 1175 · Goodenough-Kanamori-Anderson Rule · Table 1 |
| SecondaryIFP-5 | M-L-M angle and magnetic assignment | AFM; not listed in Table 1; text says IFP-5 shows antiferromagnetism | Review text and Figure 4(d,e) Text · Qualitative | No verified corpus mapping | 1174 · Goodenough-Kanamori-Anderson Rule |
| SecondaryK3Fe2[PcFe-O8] | magnetisation persistence | spontaneous magnetization above 300 K; not diminished above 350 K | ZFC/FC magnetisation and hysteresis loop summary Text · Approximate | research_0267 | 1177 · 2D MOFs Films for Spintronics |
| SecondaryK3Fe2[PcFe-O8] | charge-carrier mobility | approximately 15 cm2/V/s at 300 K | Contact-free time-resolved THz spectroscopy at 300 K Text · Approximate | research_0267 | 1177 · 2D MOFs Films for Spintronics |
| SecondaryK3Fe2[PcFe-O8] | magnetoresistance temperature range | MR observed under -6 to 6 T up to 300 K | Applied field -6 to 6 T at different temperatures Text · Exact Reported | research_0267 | 1177 · 2D MOFs Films for Spintronics |
| SecondaryRe3C12N12H12 | spin-flip and band gaps | DeltaE1 = 0.27 eV; DeltaE2 = 0.19 eV; DeltaE3 = 0.15 eV; energy gap 0.97 eV | Theoretical DOS/band-structure benchmark summarised in Figure 7 discussion Text · Exact Reported | No verified corpus mapping | 1176 · 2D MOFs Films for Spintronics |
| SecondaryRe3C12N12H12 | predicted Curie temperature | above 330 K | First-principles theoretical estimate summarised by review Text · Approximate | No verified corpus mapping | 1176 · 2D MOFs Films for Spintronics |
| SecondaryRe3C12O12 | predicted Curie temperature | above 180 K | First-principles theoretical estimate summarised by review Text · Approximate | No verified corpus mapping | 1176 · 2D MOFs Films for Spintronics |
| Secondaryredox-active ligand MOFs | electrical conductivity | as high as 20 S/m | Review summary for pyrazine and dihydroxybenzoquinone ligand MOFs Text · Approximate | research_0186 | 1172 · Introduction |
| SecondaryCr-, Fe- and Co-based naphthalene-coordinated 2D MOFs | calculated spin-filtering efficiency | Fe and Cr exhibited significant 100% spin-filtering efficiency | Two-probe spin-polarized transport calculations Text · Approximate | No verified corpus mapping | 1178 · 2D MOFs Films for Spintronics |
| SecondaryMIL-77 | M-L-M angle and magnetic assignment | FM; 97.1-99.9 degrees | Table 1 review benchmark Table · Range | No verified corpus mapping | 1175 · Goodenough-Kanamori-Anderson Rule · Table 1 |
Open questions are presented as review-author priorities, not conclusions from the primary database.
MOF thin films need reduced defects, high crystallinity and large-area fabrication to improve spin-polarized charge injection/ejection.
Proposed direction: Optimise synthetic and fabrication processes for device-quality thin films.
1179 · Conclusion
The review states that achieving ferromagnetism at high temperatures in spintronic MOFs remains challenging.
Proposed direction: Exploit pi-d hybridisation and magnetic anisotropy in 2D MOFs to raise Tc.
1176 · 2D MOFs Films for Spintronics
The review calls for improving MR or SFE and raising operating temperature over room temperature.
Proposed direction: Combine theoretical prediction and thin-film/device optimisation to improve MR/SFE at and above room temperature.
1180 · Conclusion
Most MOF charge transport has been measured with pressed pelletised powder samples, leaving actual single-crystalline thin-film transport unclear.
Proposed direction: Use single-crystalline MOF thin films to clarify charge/spin transport mechanisms.
1179 · Conclusion
Many MOFs remain unstable under ambient, solvent, acidic or alkaline conditions and are mechanically fragile.
Proposed direction: Synthesise thermally, chemically and mechanically robust MOFs compatible with nanoscale fabrication and lithography.
1181 · Conclusion
The review relies substantially on predicted magnetoelectronic properties for 2D MOFs, implying a need for experimental confirmation in single-crystalline networks.
Proposed direction: Promote theory-guided synthesis and measurement of predicted 2D MOF spin filters.
1179 · Conclusion
Mappings show which printed review references have a verified counterpart in the frozen primary corpus.
| Reference | Study | Role and context | Corpus mapping |
|---|---|---|---|
| Ref. 232018 | Title unavailable | conductive_mof_context · 2d_mof_spintronics_rationaleSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | research_0045 |
| Ref. 242020 | Title unavailable | organic_spin_valve · transport_benchmark · 2d_mof_deviceSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | research_0129 |
| Ref. 302015 | Title unavailable | redox_active_ligand · conductivity_contextSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | research_0186 |
| Ref. 312018 | Title unavailable | redox_active_ligand · magnetic_exchangeSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |
| Ref. 322018 | Title unavailable | 2d_mof_review · thin_film_fabrication_contextSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |
| Ref. 352019 | Title unavailable | transport_benchmark · room_temperature_magnetism · phthalocyanine_2d_mofSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | research_0267 |
| Ref. 402012 | Title unavailable | magnetic_mof_example · gka_interpretation · transport_benchmarkSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |
| Ref. 412014 | Title unavailable | magnetic_mof_example · gka_interpretation · transport_benchmarkSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |
| Ref. 432020 | Title unavailable | mof_magnet_review · magnetic_design_contextSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |
| Ref. 452003 | Title unavailable | magnetic_mof_example · transport_benchmark · m_l_m_angle_contextSelected because Table 1 uses this cited study for the MIL-77 ferromagnetic M-L-M angle benchmark. | Unmapped |
| Ref. 462015 | Title unavailable | gas_modulated_magnetism · transport_benchmarkSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |
| Ref. 562012 | Title unavailable | conductive_2d_mof_originSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |
| Ref. 582020 | Title unavailable | theoretical_prediction · transport_benchmark · spin_filter_deviceSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |
| Ref. 592015 | Title unavailable | theoretical_prediction · spin_filter_efficiency · 2d_mof_superlatticeSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |
| Ref. 602016 | Title unavailable | theoretical_prediction · spin_filter_efficiency · bdt_2d_mofSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |
| Ref. 612017 | Title unavailable | layered_inorganic_comparator · tc_contextSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |
| Ref. 622014 | Title unavailable | layered_inorganic_comparator · tc_contextSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |
| Ref. 662020 | Title unavailable | spintronics_outlook · application_contextSelected because the review uses this cited study for chapter-relevant MOF magnetism, conductive 2D MOF, or spintronic-device evidence. | Unmapped |