Wang J., Chen T., Jeon M. et al. · Journal of the American Chemical Society · 2024 · 20500-20507
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.
Ni3(HITT)2 and Cu3(HITT)2 are isostructural 2D hexagonal frameworks with fully eclipsed stacking and similar interlayer distances.
Caveat: Assignments are based on Pawley refinements and cryo-HRTEM; no CIF was assigned for extraction.
20502 · Results and discussion · Figure 2 · Linked to 6 structured results
The Cu2+/Cu+ ratio significantly affects Cu3(HITT)2 conductivity; ambient air oxidation converts Cu+-rich material toward Cu2+-rich material and reduces conductivity by nearly four orders of magnitude.
Caveat: Conductivity ageing was measured on pressed-pellet devices; individual-device traces are graphical in SI Figures S31-S32, while main text provides summary values.
20505 · Conclusions · Linked to 5 structured results
Ni3(HITT)2 shows about two orders of magnitude higher room-temperature conductivity than Cu3(HITT)2, attributed to stronger Ni-HITT electronic interaction, enhanced pi-d conjugation and greater Ni contribution to frontier bands.
Caveat: Transport in pellets is still dominated by defects, grain boundaries and interparticle hopping, so intrinsic metallicity is inferred rather than directly measured.
20505 · Conclusions · Linked to 4 structured results
Cu+ precursors improve Cu3(HITT)2 crystallinity, likely because their low solubility slows MOF nucleation relative to rapidly reacting solvated Cu2+ ions.
Caveat: Mechanistic statement is inferred from precursor screens and prior literature, not direct nucleation-rate measurement.
20502 · Results and discussion · Figures S13-S14 · Linked to 2 structured results
DFT suggests air oxidation of Cu3(HITT)2 widens the in-plane band gap and narrows VB/CB dispersion, consistent with reduced conductivity and optical-gap growth.
Caveat: Oxidised model removes one electron as an approximation to air exposure.
20505 · Results and discussion · Figures S35-S37 · Linked to 6 structured results
Both materials show thermally activated transport; Cu3(HITT)2 is described by Arrhenius activation in the selected range, while Ni3(HITT)2 shows lower low-temperature activation and is consistent with 3D Mott variable-range hopping at low temperature.
Caveat: Mechanism assignment is based on fitted conductivity trends rather than single-crystal transport.
20503 · Results and discussion · Figure 3a · Linked to 4 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| Cu3(HITT)2 | Cu3(HITT)2; pristine mixed-valence description (Cu+)2(Cu2+)(HITT2-)2mixed-valent Cu+ / Cu2+ centres · HITT, from HATT.3HCl | 2D · PristineHexagonal P-62m layered framework with AA/eclipsed stacking; conductivity changes on air oxidation. | 20502 · Results and discussion · Figure 2 |
| HATP ligand model | Not specifiedHATP ligand model | 0D · Model SystemMolecular ligand orbital calculation model. | 20501 · Results and discussion · Figure S1 |
| HATT.3HCl ligand precursor | 2,3,7,8,12,13-hexaaminotricycloquinazoline trihydrochloride / HATT.3HClHATT.3HCl precursor to HITT linkers in M3(HITT)2 | 0D · UnknownMolecular ligand precursor; characterised by NMR, elemental analysis and synthetic scheme in SI. | 6-8 · Ligand synthesis procedure · Scheme on SI p6; Figures S2-S10 |
| HATT ligand model | Not specifiedHATT ligand model | 0D · Model SystemMolecular ligand orbital calculation model. | 20501 · Results and discussion · Figure S1 |
| HHTT catechol analogue ligand model | Not specifiedHHTT catechol analogue ligand model | 0D · Model SystemMolecular ligand orbital calculation model. | 20501 · Results and discussion · Figure S1 |
| Ni3(HITT)2 | Ni3(HITT)2; HITT = 2,3,7,8,12,13-hexaiminotetraazanaphthotetrapheneNi2+ centres · HITT, from HATT.3HCl | 2D · PristineHexagonal P-62m layered framework with AA/eclipsed stacking. | 20500 · Abstract |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| Air-exposed Cu3(HITT)2research_0027__mat__cu3_hitt2 | Unknown · Target Sample · Unknown | Pristine Cu3(HITT)2 exposed to ambient atmosphere for 1-83 days.ambient atmosphere exposure of devices/powders depending on measurement | 20505 · Results and discussion · Figure 5 |
| DFT model of oxidised Cu3(HITT)2research_0027__mat__cu3_hitt2 | Model · Model System · Model | Air-exposed Cu3(HITT)2 modelled by removing one electron from pristine Cu3(HITT)2. | 20505 · Results and discussion · Figures S35-S37 |
| DFT model of pristine Cu3(HITT)2research_0027__mat__cu3_hitt2 | Model · Model System · Model | Pristine periodic model for band structure and DOS. | 20504 · Results and discussion · Figure 4 |
| Pristine Cu3(HITT)2 black powderresearch_0027__mat__cu3_hitt2 | Powder · Target Sample · Pristine Framework | As-synthesised, washed, vacuum-dried at room temperature; pristine mixed-valence Cu+-rich state. | 8 · Cu3(HITT)2 synthesis |
| Pressed pellet four-probe device of pristine Cu3(HITT)2research_0027__mat__cu3_hitt2 | Pellet · Target Sample · Pristine Framework | MOF powder pressed at approximately 1 GPa for 5 min, cut into cuboid, contacted with copper wires/carbon paste.dry glass slide for room-temperature device; PPMS puck for VT device · Measured after measurement using a micrometer; not numerically reported. | 3-4 · Room temperature electrical conductivity measurements · Figure S28 |
| HATP ligand modelresearch_0027__mat__hatp_ligand_model | Model · Model System · Model | B3LYP/def2-SVP molecular orbital calculation for ligand design. | 9 · Figure S1 · Figure S1 |
| HATT.3HCl ligand precursorresearch_0027__mat__hatt_3hcl_ligand_precursor | Powder · Paper Level Unspecified · Unknown | Orange solid ligand precursor dried at 60 deg C under vacuum after acid deprotection and washing. | 7-8 · 2,3,7,8,12,13-hexaaminotricycloquinazoline trihydrochloride (6) · Figure S8 |
| HATT ligand modelresearch_0027__mat__hatt_ligand_model | Model · Model System · Model | B3LYP/def2-SVP molecular orbital calculation for ligand design. | 9 · Figure S1 · Figure S1 |
| HHTT catechol analogue ligand modelresearch_0027__mat__hhtt_ligand_model | Model · Model System · Model | B3LYP/def2-SVP molecular orbital calculation for ligand design. | 9 · Figure S1 · Figure S1 |
| Air-exposed Ni3(HITT)2 controlresearch_0027__mat__ni3_hitt2 | Unknown · Target Sample · Pristine Framework | Ni3(HITT)2 exposed to air for a similar duration to Cu3(HITT)2 ageing tests.ambient atmosphere exposure of devices/powders depending on measurement | 20504 · Results and discussion · Figure 5a / Figure S33 |
| DFT model of pristine Ni3(HITT)2research_0027__mat__ni3_hitt2 | Model · Model System · Model | Pristine periodic model for band structure and DOS. | 20504 · Results and discussion · Figure 4 |
| Pristine Ni3(HITT)2 black powderresearch_0027__mat__ni3_hitt2 | Powder · Target Sample · Pristine Framework | As-synthesised, washed, vacuum-dried at room temperature. | 8 · Ni3(HITT)2 synthesis |
| Pressed pellet four-probe device of Ni3(HITT)2research_0027__mat__ni3_hitt2 | Pellet · Target Sample · Pristine Framework | MOF powder pressed at approximately 1 GPa for 5 min, cut into cuboid, contacted with copper wires/carbon paste.dry glass slide for room-temperature device; PPMS puck for VT device · Measured after measurement using a micrometer; not numerically reported. | 3-4 · Room temperature electrical conductivity measurements · Figure S28 |