Aubrey M.L., Kapelewski M.T., Melville J.F. et al. · Journal of the American Chemical Society · 2019 · 5005-5013
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 adsorption-energy calculations indicate that both acetylene and ethylene physisorption in Cu[Ni(pdt)2] is favourable.
Caveat: Adsorption free energies were not calculated; BSSE correction may overcorrect according to the authors.
SI p.S-28 · Adsorption energies · Table S8 · Linked to 3 structured results
For the tested hydrocarbons, conductance modulation is not controlled simply by binding strength or total adsorption capacity; the conductivity-composition sensitivity correlates better with gas-phase heat capacity, except for anomalous cis-2-butene.
Caveat: cis-2-Butene violates the heat-capacity trend, which the authors attribute to possible nanoconfinement and surface adsorption effects.
main p.5011 · Conclusions · Table 1; Figure 5 · Linked to 5 structured results
Conductivity is strongly sensitive to guest solvation state: acetonitrile-loaded Cu[Ni(pdt)2].xCH3CN is about 200 times less conductive than the evacuated material.
main p.5011 · Conclusions · Linked to 3 structured results
Bare Cu[Ni(pdt)2] and the C2H2/C2H4 host-guest complexes show no sizeable electronic-structure differences, so the chemiresistive response is not explained by a major band-structure change.
Caveat: The conclusion is computational and limited to acetylene and ethylene host-guest models.
main p.5010 · Electronic Structure Determinations · Figures S24-S33 · Linked to 2 structured results
Bulk conductivity in Cu[Ni(pdt)2] is consistent with nearest-neighbour charge hopping via small polarons localised on [Ni(pdt)2]2- units, although the exact charge-carrier identity was not reliably determined.
Caveat: The authors explicitly state that the exact identity of charge carriers could not be reliably determined experimentally or theoretically.
main p.5008 · Hopping Charge Transport in Cu[Ni(pdt)2] · Figure S3; Figure S24 · Linked to 3 structured results
The faster conductance equilibration relative to bulk adsorption suggests that grain or interparticle contact resistances limit pressed-pellet conduction and dominate the chemiresistive response.
Caveat: Presented by the authors as one possible explanation for the different equilibration behaviour.
main p.5011 · Kinetics Analysis of Adsorption and Conductance upon Gas Dosing · Figure 6 · Linked to 2 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| C2H2@Cu[Ni(pdt)2] | C2H2@Cu[Ni(pdt)2]Cu/Ni framework model with acetylene in the pores. · 2,3-pyrazinedithiolate plus adsorbed acetylene. | 3D · Model SystemGuest-loaded powder diffraction structure and DFT model with acetylene centred along the pore axis. | main p.5009 · Determination of Guest-Adsorbed Structures · Figure 4 |
| C2H4@Cu[Ni(pdt)2] | C2H4@Cu[Ni(pdt)2]Cu/Ni framework model with ethylene in the pores. · 2,3-pyrazinedithiolate plus adsorbed ethylene. | 3D · Model SystemGuest-loaded powder diffraction structure and DFT model with ethylene centred along the pore axis. | main p.5009 · Determination of Guest-Adsorbed Structures · Figure 4 |
| Cu[Ni(pdt)2] | Cu[Ni(C4H2N2S2)2] / Cu[Ni(pdt)2], pdt = pyrazine-2,3-dithiolateSquare-planar Cu(II) centers linked to square-planar nickel(II) pyrazine-2,3-dithiolate units. · 2,3-pyrazinedithiolate (pdt2-) / pyrazine-2,3-dithiolate. | 3D · PristinePermanently porous 3D conductive framework, isostructural to Cu[Cu(pdt)2], with square channels and P42/mmc diffraction refinements. | main p.5007 · Results and Discussion · Figure 1 |
| Cu[Ni(pdt)2].xCH3CN | Cu[Ni(pdt)2].xCH3CNSame Cu/Ni framework as Cu[Ni(pdt)2]. · 2,3-pyrazinedithiolate with acetonitrile guest inclusion. | 3D · PristineGuest-included acetonitrile-solvated phase used to probe solvation-state effects on conductivity. | main p.5008 · Hopping Charge Transport in Cu[Ni(pdt)2] |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| Activated Cu[Ni(pdt)2] powderresearch_0052__mat__cu_ni_pdt | Powder · Target Sample · Pristine Framework | Dark red microcrystalline powder activated overnight at 90 C under high vacuum. | main p.5006 · Modified Synthesis of Cu[Ni(pdt)2] |
| C2H2-dosed Cu[Ni(pdt)2] capillary PXRD sampleresearch_0052__mat__c2h2_cu_ni_pdt_model | Powder · Target Sample · Guest Loaded | Fully desolvated framework loaded in N2 glovebox, evacuated, and dosed with C2H2 at 20-1077 mbar.1.0 mm borosilicate capillary | SI p.S-9 · Structure Determination by Powder X-ray Diffraction · Table S3 |
| C2H4-dosed Cu[Ni(pdt)2] capillary PXRD sampleresearch_0052__mat__c2h4_cu_ni_pdt_model | Powder · Target Sample · Guest Loaded | Fully desolvated framework loaded in N2 glovebox, evacuated, and dosed with C2H4 at 24-985 mbar.1.0 mm borosilicate capillary | SI p.S-9 · Structure Determination by Powder X-ray Diffraction · Table S4 |
| Acetonitrile-vapour exposed Cu[Ni(pdt)2].xCH3CNresearch_0052__mat__cu_ni_pdt_ch3cn | Pellet · Target Sample · Guest Loaded | Cu[Ni(pdt)2] exposed to saturated acetonitrile vapour at room temperature for 12 h. | main p.5008 · Hopping Charge Transport in Cu[Ni(pdt)2] |
| Loose Cu[Ni(pdt)2] powder for adsorption isothermsresearch_0052__mat__cu_ni_pdt | Powder · Target Sample · Pristine Framework | Powder loaded into preweighed tube and heated at 90 C overnight before adsorption measurements. | main p.5006 · Gas Adsorption Measurements |
| Hydrocarbon-dosed Cu[Ni(pdt)2] pelletresearch_0052__mat__cu_ni_pdt | Pellet · Target Sample · Guest Loaded | Pressed pellet dosed with pure-component hydrocarbon gases under constant-current conditions.Copper traces on printed circuit board in gas adsorption analyser cell. · 50-100 um | main p.5009 · Modulation of Conductivity upon Gas Adsorption · Figure 3 |
| DFT model of pristine Cu[Ni(pdt)2]research_0052__mat__cu_ni_pdt | Model · Model System · Model | Periodic DFT model of the bare framework. | SI p.S-24 · Electronic Structure Calculations |
| DFT model of C2H2@Cu[Ni(pdt)2]research_0052__mat__c2h2_cu_ni_pdt_model | Model · Model System · Model | Periodic DFT model with acetylene adsorbates. | main p.5007 · Computational Methods |
| DFT model of C2H4@Cu[Ni(pdt)2]research_0052__mat__c2h4_cu_ni_pdt_model | Model · Model System · Model | Periodic DFT model with ethylene adsorbates. | SI p.S-24 · Electronic Structure Calculations |
| Pressed-pellet Cu[Ni(pdt)2] transport sampleresearch_0052__mat__cu_ni_pdt | Pellet · Target Sample · Pristine Framework | Activated powder mechanically pressed between copper rails/traces in an Ar-filled glovebox.Two copper traces on FR-4 printed circuit board, or two-contact PEEK screw cell for ac impedance. · 50-100 um for gas-cell pellet; about 50 um in method description | main p.5008 · Hopping Charge Transport in Cu[Ni(pdt)2] · Figure 2 |