Kobayashi Y., Jacobs B., Allendorf M.D. et al. · Chemistry of Materials · 2010 · 4120-4122
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Paraphrased for this database from the authors’ stated interpretations — never quoted verbatim — and kept separate from reported measurements.
Cu[Ni(pdt)2] combines permanent microporosity with electronic conductivity.
Caveat: Pristine conductivity is low; high conductivity requires iodine oxidation.
1 · Introduction and porosity · Figure 2 · Linked to 4 structured results
Cu[Cu(pdt)2] is isostructural with Cu[Ni(pdt)2] when solvated but loses its porous framework on desolvation.
Caveat: Porosity for Cu[Cu(pdt)2] was not explicitly demonstrated by gas adsorption in this paper.
1 · Structure comparison · Figure S1 · Linked to 2 structured results
Changing the dithiolate-complex metal from copper to nickel tunes the framework optical bandgap.
Caveat: Cu[Cu(pdt)2] bandgap is not numerically reported in text; comparison value is a visual estimate from Figure S3.
3 · Conclusion · Figure S3 · Linked to 2 structured results
Framework redox peak separation and anion-size dependence indicate rate-limiting diffusion of charge-balancing or electroactive species through pores.
Caveat: Supported by qualitative CV comparisons rather than extracted diffusion coefficients.
3 · Electrochemistry discussion · Figure 4 · Linked to 2 structured results
The enhanced conductivity is attributed primarily to the MOF framework rather than bulk iodine conduction.
Caveat: The exact iodine content is not quantified beyond no significant gravimetric gain.
2 · Iodine uptake check · Linked to 3 structured results
Oxidative iodine doping increases conductivity and supports assigning Cu[Ni(pdt)2] as a p-type semiconductor.
Caveat: Dopant amount is very small and doping is partly reversible on air exposure.
2 · Iodine doping · Figure 3 · Linked to 3 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| Cu[Cu(pdt)2] | Cu[Cu(pdt)2]; pdt2- = pyrazine-2,3-dithiolateCu connector units and copper bis-dithiolate units · Pyrazine-2,3-dithiolate (pdt2-) ligand | 3D · PristineIsostructural Cu analogue used as comparison; SI assigns the same P42/mmc unit-cell family before desolvation. | 1 · Main text |
| Cu[Ni(pdt)2] | CuNiC8H4N4S4 after desolvation; pdt2- = pyrazine-2,3-dithiolateSquare-planar Cu(pyrazine)4 connector units and redox-active nickel bis-dithiolate units · Pyrazine-2,3-dithiolate (pdt2-) ligand | 3D · PristineTetragonal metal-organic framework with one-dimensional channels; powder X-ray diffraction gives P42/mmc unit-cell assignment in the SI. | 1 · Main text · Figure 1 |
| [Cu(pdt)2]2-/1- molecular redox couple | [Cu(pdt)2]2-/1-Molecular Cu bis-dithiolate complex · Pyrazine-2,3-dithiolate (pdt2-) | 0D · Model SystemSolution molecular reference for the Cu[Cu(pdt)2] framework. | 3 · Electrochemistry discussion · Figure 4 |
| n-doped Si(111) reference electrode | n-Si(111) | 0D · Model SystemNon-MOF semiconductor reference used only for photocurrent polarity comparison. | 8 · Photocurrent Experiments · Figure S4 |
| [Ni(pdt)2]2-/1- molecular redox couple | [Ni(pdt)2]2-/1-Molecular Ni bis-dithiolate complex · Pyrazine-2,3-dithiolate (pdt2-) | 0D · Model SystemSolution molecular reference for framework redox behaviour. | 1 · Main text · Figure 1 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| As-prepared Cu[Cu(pdt)2] powderresearch_0203__mat__cu_cu_pdt2 | Powder · Pristine Control · Guest Loaded | Cu analogue prepared by the analogous framework route; rough micron-sized particles. | 3 · Cu[Ni(pdt)2] and Cu[Cu(pdt)2] · Figure S5 |
| Desolvated Cu[Cu(pdt)2] powderresearch_0203__mat__cu_cu_pdt2 | Powder · Pristine Control · Pristine Framework | Cu[Cu(pdt)2] after 120 degC vacuum treatment. | 1 · Main text · Figure S1 |
| Cu[Cu(pdt)2] particles cast on Pt disk electroderesearch_0203__mat__cu_cu_pdt2 | Electrode · Pristine Control · Pristine Framework | Suspension of micron-sized Cu[Cu(pdt)2] particles cast onto a Pt disk electrode for cyclic voltammetry.Pt disk electrode | 3 · Electrochemistry · Figure 4 |
| Air-exposed I2-doped Cu[Ni(pdt)2] filmresearch_0203__mat__cu_ni_pdt2 | Thin Film · Target Sample · Doped | I2-doped film exposed to air for 12 h.Pt interdigitated electrode on glass · on the order of a few microns | 2 · Iodine doping |
| Desolvated Cu[Ni(pdt)2] powderresearch_0203__mat__cu_ni_pdt2 | Powder · Target Sample · Pristine Framework | Solvated powder heated at 120 degC under dynamic vacuum to remove pore guests. | 1 · Activation and porosity · Figures 2, S1, S2 |
| I2-doped Cu[Ni(pdt)2] film at 150 degCresearch_0203__mat__cu_ni_pdt2 | Thin Film · Target Sample · Doped | Evacuated Cu[Ni(pdt)2] film treated with iodine vapour at 150 degC.Pt interdigitated electrode on glass · on the order of a few microns | 2 · Iodine doping · Figure 3 |
| I2-doped Cu[Ni(pdt)2] film at 50 degCresearch_0203__mat__cu_ni_pdt2 | Thin Film · Target Sample · Doped | Evacuated Cu[Ni(pdt)2] film treated with flowing N2/I2 vapour at 50 degC while conductivity was recorded.Pt interdigitated electrode on glass · on the order of a few microns | 2 · Iodine doping · Figure 3 |
| Cu[Ni(pdt)2] powder exposed to I2 vapour for gravimetryresearch_0203__mat__cu_ni_pdt2 | Powder · Target Sample · Doped | 100 mg powder sample exposed to the same iodine vapour stream for 4 h. | 2 · Iodine uptake check |
| Cu[Ni(pdt)2] film on Pt interdigitated electroderesearch_0203__mat__cu_ni_pdt2 | Thin Film · Target Sample · Pristine Framework | Cu[Ni(pdt)2] suspension evaporated on IDE; sample desolvated before conductivity measurement.Pt interdigitated electrode on glass · on the order of a few microns | 3-4 · Preparation of Cu[Ni(pdt)2] electrodes |
| Cu[Ni(pdt)2]/ITO photoelectroderesearch_0203__mat__cu_ni_pdt2 | Electrode · Target Sample · Pristine Framework | Cu[Ni(pdt)2] deposited on ITO slides in a manner similar to the IDE films.ITO slide · on the order of a few microns, by analogy to IDE films | 4 · Preparation of Cu[Ni(pdt)2] electrodes |
| Cu[Ni(pdt)2] particles cast on Pt disk electroderesearch_0203__mat__cu_ni_pdt2 | Electrode · Target Sample · Pristine Framework | Suspension of 150 nm Cu[Ni(pdt)2] particles cast onto a Pt disk electrode for cyclic voltammetry.Pt disk electrode | 3 · Electrochemistry · Figure 4 |
| As-synthesised solvated Cu[Ni(pdt)2] powderresearch_0203__mat__cu_ni_pdt2 | Powder · Target Sample · Guest Loaded | Dark red colloid/precipitate isolated from acetonitrile on a 0.22 um nylon membrane filter. | 3 · Cu[Ni(pdt)2] and Cu[Cu(pdt)2] |
| [Cu(pdt)2]2-/1- solution CV sampleresearch_0203__mat__cu_pdt2_solution_complex | Model · Model System · Model | Tetra-n-butylammonium salt in acetonitrile. | 3 · Electrochemistry discussion · Figure 4 |
| n-Si(111) photocurrent referenceresearch_0203__mat__n_si_reference | Electrode · Model System · Model | n-Si cleaned in buffered oxide etch before photocurrent measurement. | 4-5 · Photocurrent Measurements · Figure S4 |
| [Ni(pdt)2]2-/1- solution CV sampleresearch_0203__mat__ni_pdt2_solution_complex | Model · Model System · Model | Molecular redox couple in solution. | 1 · Main text |