Yadav A., Zhang S., Benavides P.A. et al. · Angewandte Chemie - International Edition · 2023 · e202303819
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 authors caution that band-structure calculations for MOFs containing non-coordinated guest molecules are challenging, and more sophisticated structural models may be needed for a fully accurate picture.
7 · Results and Discussion · Figure 6 and Figure S18 · Linked to 2 structured results
Retention of most Cu3(HATP)2 porosity supports HCTP being stacked in the framework walls rather than occupying the hexagonal channels.
Caveat: Porosity is indirect evidence and relies on comparison with the structural model.
4 · Results and Discussion · Figure S8 · Linked to 2 structured results
The bottom-up synthesis works by preassembling a 1:1 HATP/HCTP pi-donor/acceptor array and then forming Cu3(HATP)2 layers that retain non-coordinatively intercalated HCTP between HATP units.
Caveat: The iGMOF1 structure is derived from PXRD/DFT modelling rather than single-crystal diffraction of iGMOF1.
2 · Results and Discussion · Scheme 1 · Linked to 3 structured results
Pyrene and triphenylene controls do not produce analogous iGMOFs because they lack complementary donor/acceptor interaction with electron-rich HATP and are not incorporated.
Caveat: Controls are specific to pyrene and triphenylene under the reported synthesis conditions.
6 · Results and Discussion · Figures S14-S17 · Linked to 2 structured results
Post-synthetic HCTP intercalation into preformed Cu3(HATP)2 is ineffective because the short interlayer spacing prevents HCTP infiltration.
Caveat: Demonstrated for the reported HCTP/DMF soaking conditions, not all possible post-synthetic conditions.
4 · Results and Discussion · Figure S5c · Linked to 3 structured results
iGMOF1 has about an order-of-magnitude higher pellet conductivity than pristine Cu3(HATP)2 because alternate HATP/HCTP stacks add an efficient out-of-plane transport pathway while the Cu3(HATP)2 network preserves in-plane conduction.
Caveat: Transport was measured on pressed pellets, so grain-boundary resistance may depress absolute conductivity relative to single crystals.
5 · Results and Discussion · Figure 5 · Linked to 4 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| Cu3(HATP)2 | Cu3(HATP)2Square-planar Cu2+ nodes · HATP = 2,3,6,7,10,11-hexaaminotriphenylene | 2D · PristinePristine 2D graphitic Cu3(HATP)2 framework used as the primary non-intercalated control. | 3 · Results and Discussion · Figure S1 |
| Supramolecular [HATP/HCTP]n array | C42H24N12None · Alternating HATP donor and HCTP acceptor molecules | 1D · Model SystemOrganic donor/acceptor co-crystal array with alternate head-to-tail cofacial HATP/HCTP stacks along the c-axis. | S11 · Table S1 · Table S1 |
| iGMOF1 | [Cu3(HATP)2.(2HCTP)]Square-planar Cu2+ nodes · HATP = 2,3,6,7,10,11-hexaaminotriphenylene; non-coordinatively intercalated HCTP = hexacyanotriphenylene | 2D · PristinePi-intercalated graphitic MOF with 2D hexagonal Cu3(HATP)2 layers in the ab-plane and alternate HATP/HCTP donor/acceptor stacks along the c-axis; PXRD/Rietveld and DFT model support orthorhombic C2mm structure. | 3 · Results and Discussion · Figure 2 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| Post-synthetically HCTP-treated Cu3(HATP)2research_0109__mat__mat_cu3_hatp2 | Powder · Pristine Control · Pristine Framework | Cu3(HATP)2 powder soaked in 100 mM HCTP/DMF for 72 h, washed, and dried. | S4 · HCTP-Treated Cu3(HATP)2 |
| DFT model of Cu3(HATP)2research_0109__mat__mat_cu3_hatp2 | Model · Model System · Model | Periodic DFT/PBE-optimised primitive-cell model followed by HSE06 single-point band/DOS calculation. | S3 · Density Functional Theory (DFT) Calculations · Figure S18 |
| Pristine Cu3(HATP)2 pressed pelletresearch_0109__mat__mat_cu3_hatp2 | Pellet · Pristine Control · Pristine Framework | Pressed pellet prepared by the same two-probe pellet protocol as iGMOF1. | 5 · Results and Discussion · Figure 5a |
| Pristine Cu3(HATP)2 powderresearch_0109__mat__mat_cu3_hatp2 | Powder · Pristine Control · Pristine Framework | Black precipitate made from HATP.6HCl, Cu(NO3)2.3H2O, and NaOAc, then washed and vacuum dried. | S4 · Cu3(HATP)2 |
| Cu3(HATP)2 formed in the presence of pyreneresearch_0109__mat__mat_cu3_hatp2 | Pellet · Pristine Control · Pristine Framework | Cu3(HATP)2 synthesis attempted with equimolar pyrene present; washed, vacuum dried, and pressed for I-V. | S4 · Cu3(HATP)2 in the Presence of pi-Donors · Figure S16 |
| Cu3(HATP)2 formed in the presence of triphenyleneresearch_0109__mat__mat_cu3_hatp2 | Pellet · Pristine Control · Pristine Framework | Cu3(HATP)2 synthesis attempted with equimolar triphenylene present; washed, vacuum dried, and pressed for I-V. | S4 · Cu3(HATP)2 in the Presence of pi-Donors · Figure S16 |
| Supramolecular [HATP/HCTP]n array powder/crystalsresearch_0109__mat__mat_hatp_hctp_array | Powder · Model System · Model | Dark-brown 1:1 HATP/HCTP donor/acceptor array; crystals from slow DMF evaporation and powder from Et2O precipitation. | S4 · Supramolecular [HATP/HCTP]n Array |
| DFT model of iGMOF1research_0109__mat__mat_igmof1 | Model · Model System · Model | Periodic DFT/PBE-optimised primitive-cell model followed by HSE06 single-point band/DOS calculation. | S3 · Density Functional Theory (DFT) Calculations · Figure 6 |
| iGMOF1 pressed pelletresearch_0109__mat__mat_igmof1 | Pellet · Target Sample · Guest Loaded | Approximately 3.5 mg powder pressed between Ag-paint-coated stainless-steel rods at 200 MPa for 1 min for two-probe I-V measurements. | S2 · Electrical Conductivity Measurements |
| iGMOF1 black powderresearch_0109__mat__mat_igmof1 | Powder · Target Sample · Guest Loaded | Black precipitate from bottom-up self-assembly/coordination reaction, centrifuged, washed with water and acetone, and vacuum dried. | S4 · S2. Synthesis and Characterization |