Yamamoto S., Pirillo J., Hijikata Y. et al. · Chemical Science · 2018 · 3282-3289
Open a family to keep every result attached to its sample, method and conditions.
Paraphrased for this database from the authors’ stated interpretations — never quoted verbatim — and kept separate from reported measurements.
The humid I-V response is not considered an intrinsic conductivity of compounds 1 or 2 because both samples decompose and lose crystallinity after 24 h at 97% RH.
Caveat: Humid I-V curves still show linear response for 1 and hysteresis for 2.
SI p.9 · S7. Electrical conductivity · Fig. S8 · Linked to 2 structured results
The crystal-sponge loading route produced phase-pure Mn-MOF guest crystals for compounds 1 and 2.
Caveat: Compound 2 required synchrotron diffraction because initial laboratory single-crystal XRD quality was inadequate.
SI p.6 · S5. PXRD · Fig. S5 · Linked to 3 structured results
MOF nanopore confinement and even donor distribution promote donor-to-host charge transfer that does not occur in simple AQDC/donor control mixtures.
Caveat: The resulting materials remain insulating in this paper despite charge-transfer evidence.
p.8 · Conclusions · Linked to 5 structured results
TMPDA-loaded compound 2 shows a much larger charge-transfer/radical contribution than TTF-loaded compound 1.
Caveat: Charge estimates intentionally ignore possible antiferromagnetic coupling between donor, acceptor and Mn7 clusters; authors call the result qualitative.
p.6 · Experimental evidence of charge transfer · Linked to 5 structured results
The Mn-MOF guest-loading strategy is size selective; larger BEDT-TTF and TMTSF donors diffuse slowly and only surface-dope crystals, preventing isolation of phase-pure complexes.
Caveat: Detailed attempted-loading recipe for BEDT-TTF/TMTSF is not provided.
SI p.8 · S6. Selective impregnation · Table S3 · Linked to 3 structured results
TD-DFT assigns the experimental low-energy CT absorption mainly to D-A-A-D tetrameric motifs and nanopore-imposed steric geometry.
Caveat: Computational models are fragment/tetramer models, not periodic transport calculations.
SI p.18 · S11. Theoretical simulations · Fig. S17 · Linked to 3 structured results
Both reported charge-transfer Mn-MOF complexes are insulating under vacuum, with pellet conductivity below 10^-12 S/cm.
Caveat: Measured on pressed pellets, not single crystals, because donor-loaded crystals cracked.
SI p.9 · S7. Electrical conductivity · Linked to 2 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| AQDC donor reaction and computational model systems | Not specifiedNone for free ligand/donor reactions; partial Mn-AQDC model in DFT section · 2,7-AQDC, TTF, TMPDA and model D-A or D-A-A-D clusters | 0D · Model SystemControl reactions and DFT models used to compare non-MOF donor-acceptor behaviour. | p.7 · The confinement effect of the micropores · Fig. 5 |
| BEDT-TTF doped Mn-MOF attempt | Mn7(AQDC)7(DMA)6 > BEDT-TTF0.20Heptanuclear Mn(II) MOF nodes · AQDC/DMA host with surface-doped BEDT-TTF donor | 3D · UnknownAttempted donor impregnation; only surface doping observed and no phase-pure charge-transfer complex isolated. | SI p.8 · S6. Selective impregnation · Table S3 |
| Mn-MOF | {Mn7(2,7-AQDC)6(2,6-AQDC)(DMA)6}Heptanuclear Mn(II) secondary building units · 2,7-anthraquinone dicarboxylate and 2,6-anthraquinone dicarboxylate; coordinated DMA | 3D · PristineFlexible redox-active MOF with anthraquinone acceptor groups and nanochannels. | p.3 · Results and discussion - Structural perspectives |
| Mn-MOF 7TMPDA, compound 2 | {Mn7(2,7-AQDC)6(2,6-AQDC)(DMA)4(H2O)2(TMPDA)7}Heptanuclear Mn(II) secondary building units inherited from Mn-MOF · AQDC anthraquinone linkers plus seven TMPDA guest donors per Mn7 formula; two waters replace two DMA ligands | 3D · PristineGuest-loaded Mn-MOF charge-transfer complex; TMPDA donors form D-A-A-D columns and isolated D-A-A-D units. | p.2 · Abstract / Introduction |
| Mn-MOF 5TTF, compound 1 | {Mn7(2,7-AQDC)6(2,6-AQDC)(DMA)6(TTF)5}Heptanuclear Mn(II) secondary building units inherited from Mn-MOF · AQDC anthraquinone linkers plus five tetrathiafulvalene guest donors per Mn7 formula | 3D · PristineGuest-loaded Mn-MOF charge-transfer complex; TTF donors occupy Type I, II and III sites, including D-A-A-D columns. | p.2 · Abstract / Introduction |
| TMTSF doped Mn-MOF attempt | Mn7(AQDC)7(DMA)6 > TMTSF0.34Heptanuclear Mn(II) MOF nodes · AQDC/DMA host with surface-doped TMTSF donor | 3D · UnknownAttempted donor impregnation; only surface doping observed and no phase-pure charge-transfer complex isolated. | SI p.8 · S6. Selective impregnation · Table S3 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| TMPDA plus AQDC reaction residueresearch_0534__mat__aqdc_donor_model_systems | Powder · Model System · Model | AQDC ligand and TMPDA heated in hot DMF at 120 degC for 1 h, then DMF removed. | p.4 · Physical measurements |
| TTF plus AQDC reaction residueresearch_0534__mat__aqdc_donor_model_systems | Powder · Model System · Model | AQDC ligand and TTF heated in hot DMF at 120 degC for 1 h, then DMF removed. | p.4 · Physical measurements |
| BEDT-TTF doped Mn-MOF crystalsresearch_0534__mat__bedt_ttf_doped_mn_mof | Powder · Target Sample · Doped | Attempted spontaneous incorporation; diffusion slow and only crystal surface doped. | SI p.7 · S6. Selective impregnation · Fig. S7 |
| DFT models from compound 1research_0534__mat__aqdc_donor_model_systems | Model · Model System · Model | Dimer D1a/D2a and tetramer T1a models from the compound 1 crystal structure. | SI p.14 · S11. Theoretical simulations · Fig. S13 |
| DFT models from compound 2research_0534__mat__aqdc_donor_model_systems | Model · Model System · Model | Dimer D1b/D2b/D3b and tetramer T1b/T2b/T3b models from the compound 2 crystal structure. | SI p.14 · S11. Theoretical simulations · Fig. S13 |
| Free 2,7-AQDC, TTF and TMPDA in DMF electrolyteresearch_0534__mat__aqdc_donor_model_systems | Unknown · Model System · Model | Saturated DMF solutions with 1.0 mol/L tetrabutylammonium hexafluorophosphate electrolyte. | SI p.4 · S3. Cyclic voltammetry · Fig. S2 |
| As-prepared Mn-MOF crystalsresearch_0534__mat__mn_mof | Single Crystal · Pristine Control · Pristine Framework | Collected from solvothermal product, washed with hot DMF and used without solvent exchange or activation. | p.3 · Preparation of the materials |
| Compound 2 Mn-MOF 7TMPDA crystalsresearch_0534__mat__mn_mof_tmpda_2 | Single Crystal · Target Sample · Guest Loaded | Phase-pure guest crystals after CH2Cl2 guest loading and sublimation removal of excess TMPDA. | p.3 · Preparation of the materials |
| Pressed pellet of compound 2research_0534__mat__mn_mof_tmpda_2 | Pellet · Target Sample · Guest Loaded | Pressed pellet prepared because cracked crystals were unsuitable for regular single-crystal transport geometry. | SI p.9 · S7. Electrical conductivity · Fig. S8 |
| Compound 1 Mn-MOF 5TTF crystalsresearch_0534__mat__mn_mof_ttf_1 | Single Crystal · Target Sample · Guest Loaded | Phase-pure guest crystals after CH2Cl2 guest loading and sublimation removal of excess TTF. | p.3 · Preparation of the materials |
| Pressed pellet of compound 1research_0534__mat__mn_mof_ttf_1 | Pellet · Target Sample · Guest Loaded | Pressed pellet prepared because cracked crystals were unsuitable for regular single-crystal transport geometry. | SI p.9 · S7. Electrical conductivity · Fig. S8 |
| TMTSF doped Mn-MOF crystalsresearch_0534__mat__tmtsf_doped_mn_mof | Powder · Target Sample · Doped | Attempted spontaneous incorporation; diffusion slow and only crystal surface doped. | SI p.7 · S6. Selective impregnation · Fig. S7 |