Chong S., Rogge S.M.J., Kim J. · Chemistry of Materials · 2022 · 254-265
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.
DFT+U sensitivity calculations change the absolute CBM dispersions but preserve the qualitative transition from 1D to 2D charge transport between lp and np phases.
Caveat: U parameters were literature values rather than system-specific validated parameters.
S39 · Calculations at the DFT+U Theory-Level · Table S4 · Linked to 3 structured results
The proposed M(NDIDP) frameworks are in silico model systems; the NDI-containing linkers incorporated into M(NDIDP) had not yet been synthesised.
Caveat: No experimental synthesis routes or measured conductivity values are reported for M(NDIDP) in this paper.
256 · Results and Discussion - Modular Design of M(NDIDP)
Large VBM dispersions, especially in Fe(NDIDP), are likely DFT artefacts and should not be treated as reliable evidence of efficient hole transport.
Caveat: The authors attribute Fe VBM dispersion to overestimated Fe-Fe interactions/spin coupling.
S31 · VBM Dispersion in M(NDIDP) · Figure S26
Zn(NDIDP) and Co(NDIDP) have two mechanically stable branches at room temperature, enabling low-positive-pressure lp-to-np transitions, while Fe(NDIDP) has only the np phase thermodynamically stable at atmospheric pressure.
Caveat: Negative-pressure np-to-lp transitions are described as not yet practically achieved in MOFs.
258 · Flexibility of M(NDIDP): Pressure vs Volume Equation of State · Figure 4 · Linked to 3 structured results
Replacing the benzene unit in flexible M(BDP)-type wine-rack frameworks with redox-active NDI moieties creates model MOFs that combine framework flexibility with predicted conductive charge-transport pathways.
Caveat: Conductivity is inferred from calculated CBM dispersion/effective mass and would require electron population by excitation or n-doping.
259 · Electrical Conductivity of M(NDIDP) and Configuration-Dependent CT · Linked to 3 structured results
Double methylation in Zn(NDIDP)-CH3 strongly hinders framework flexibility, increasing the lp-to-np pressure requirement while still allowing improved CT if the np phase is accessed.
Caveat: The Zn(NDIDP)-CH3 np phase is computationally predicted and not experimentally reported.
S28 · Flexibility and Conductivity of Zn(NDIDP)-CH3 · Figures S21-S23 · Linked to 3 structured results
Compressing Co(NDIDP) past the np phase into the sq configuration gives the strongest predicted CT enhancement, with 738 meV Gamma-Z CBM dispersion and 0.37m0 effective mass.
Caveat: The sq configuration is not thermodynamically accessible under ambient conditions in the reported model and would need external stabilisation.
261 · Further Exploration of Configuration-Dependent CT · Figure 6 · Linked to 3 structured results
M(NDIDP)-lp supports mainly 1D charge transport along the z-axis, whereas M(NDIDP)-np introduces 2D transport through herringbone NDI packing in the xz-plane.
Caveat: Based on band dispersion and NDI packing analysis, not direct transport measurement.
260 · Electrical Conductivity of M(NDIDP) and Configuration-Dependent CT · Table 1 · Linked to 3 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| Co(NDIDP) | Co(NDIDP); NDIDP = N,N-di(1H-pyrazol-4-yl)-1,4,5,8-naphthalenediimideCo 1D metal pyrazolate pillars · NDIDP bidentate pyrazolate linker with central NDI moiety | 3D · Model SystemFlexible wine-rack MOF model with exp, lp, int1, int2, np, and sq configurations. | 256 · Results and Discussion - Modular Design of M(NDIDP) · Figure 1c |
| Fe(NDIDP) | Fe(NDIDP); NDIDP = N,N-di(1H-pyrazol-4-yl)-1,4,5,8-naphthalenediimideFe 1D metal pyrazolate pillars · NDIDP bidentate pyrazolate linker with central NDI moiety | 3D · Model SystemFlexible wine-rack MOF model with lp, np, exp, sq, and secondary sheared configurations. | 257 · Flexibility of M(NDIDP): Energy vs Volume Profile · Figure 2 |
| Zn(NDIDP) | Zn(NDIDP); NDIDP = N,N-di(1H-pyrazol-4-yl)-1,4,5,8-naphthalenediimideZn 1D metal pyrazolate pillars · NDIDP bidentate pyrazolate linker with central naphthalene diimide (NDI) moiety | 3D · Model SystemFlexible wine-rack MOF model with lp, np, exp, and sq configurations. | 256 · Results and Discussion - Modular Design of M(NDIDP) · Figure 1c |
| Zn(NDIDP)-CH3 | methylated Zn(NDIDP)-CH3 analogueZn 1D metal pyrazolate pillars · Methylated pyrazolate NDI linker with methyl groups at the 3 and 5 positions | 3D · Model SystemComputational comparator corresponding to methylated Zn pyrazolate NDI MOF. | S26 · Flexibility and Conductivity of Zn(NDIDP)-CH3 · Figure S20 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| Co(NDIDP) computational modelresearch_0384__mat__mat_condidp | Model · Model System · Model | DFT-optimised and MD-simulated model configurations | 255 · Methods - DFT Calculations |
| Fe(NDIDP) computational modelresearch_0384__mat__mat_fendidp | Model · Model System · Model | DFT-optimised and MD-simulated model configurations | 255 · Methods - DFT Calculations |
| Zn(NDIDP)-CH3 computational modelresearch_0384__mat__mat_zndidp_ch3 | Model · Model System · Model | DFT and MD computational comparator | S26 · Flexibility and Conductivity of Zn(NDIDP)-CH3 · Figure S20 |
| Zn(NDIDP) computational modelresearch_0384__mat__mat_zndidp | Model · Model System · Model | DFT-optimised and MD-simulated model configurations | 255 · Methods - DFT Calculations |