Gupta S., Tanaka H., Sato T. et al. · Inorganic Chemistry · 2022 · 4414-4420
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 claim this is the first example of changing the conduction-carrier type by postsynthetic carrier doping in a MOF.
Caveat: This is an author novelty claim, not independently verified in this extraction.
5 · Thermoelectric Properties · Figure 6 · Linked to 2 structured results
Bromine vapour doping retains the intrinsic Cu[Cu(pdt)2] framework structure while altering unit-cell parameters.
Caveat: PXRD averages cannot distinguish class-II versus class-III mixed-valence distributions.
2-3 · Results and Discussion · Figure 2 · Linked to 3 structured results
Brx@Cu[Cu(pdt)2] remains semiconductive rather than metallic after bromine doping, consistent with a segregated valence-state formulation.
Caveat: IVCT assignment of the low-energy band is proposed but explicitly requires further study.
4 · UV-vis-NIR Spectra · Figure 4 · Linked to 2 structured results
Br2 vapour oxidises [CuII(pdt)2]2- to [CuIII(pdt)2]- in the host framework, causing Cu-S contraction and c-axis shortening.
Caveat: The authors state Br-/Br2/Br3- speciation cannot be fully confirmed by Raman because host peaks overlap.
3 · Results and Discussion · Figure 3 · Linked to 6 structured results
Bromine doping increases electrical conductivity by about an order of magnitude, probably via band filling and redox hopping between partially oxidised CuII/CuIII centres.
Caveat: Exact doped-sample conductivity values are graph-read except for the pristine value; authors note possible charge ordering but have no direct arrangement data.
4 · Electrical Conductivity · Figure 5; Figure S5 · Linked to 4 structured results
The same Cu[Cu(pdt)2] framework changes from p-type to n-type thermoelectric response as bromine fraction increases, with Seebeck sign reversal near x = 0.5.
Caveat: Doped Seebeck magnitudes are visual estimates from Figure 6b; the sign-change boundary is stated in text.
5 · Thermoelectric Properties · Figure 6 · Linked to 4 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| Brx@Cu[Cu(pdt)2] | Brx@Cu[Cu(pdt)2], represented by authors as Brx-@CuII[CuII(pdt)2]1-x[CuIII(pdt)2]x for the segregated semiconductive stateCopper centres partially oxidised from CuII to CuIII in the Cu(pdt)2 moiety · 2,3-pyrazinedithiolate (pdt) | 3D · PristineBromine-loaded/doped isomorphic derivative of Cu[Cu(pdt)2] with retained crystallinity and continuously shortened c axis with increasing x. | 2-3 · Results and Discussion · Figure 2; Table S1 |
| Cu[Cu(pdt)2] | Cu[Cu(pdt)2] (pdt = 2,3-pyrazinedithiolate)Copper centres; pristine oxidation-state description CuII[CuII(pdt)2] · 2,3-pyrazinedithiolate (pdt) | 3D · PristineTetragonal P42/mmc conductive MOF with 1D pores, pore diameter about 3.4 A; structure shown by prior crystal model and PXRD retained after bromine doping. | 1-2 · Introduction; Experimental Section · Figure 1 |
| [Cu(pdt)2] redox model species | [CuII(pdt)2]2- and [CuIII(pdt)2]-Molecular copper dithiolene centres · 2,3-pyrazinedithiolate (pdt) | 0D · Model SystemIsolated molecular species used in DFT calculations to interpret Raman shifts and Cu-S bond contraction. | 3 · Results and Discussion · Figure 2c; Figure 3 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| Br0.08@Cu[Cu(pdt)2]research_0718__mat__mat_br_cu_cu_pdt2 | Powder · Target Sample · Doped | Elemental-analysis and Le Bail sample with x = 0.08.none | S3 · Table S1/S2 · Table S1; Table S2 |
| Br0.10@Cu[Cu(pdt)2]research_0718__mat__mat_br_cu_cu_pdt2 | Pellet · Target Sample · Doped | Transport/thermoelectric figure sample labelled x = 0.10; likely a rounded low-doping sample distinct from SI table x = 0.08.none · typically 0.05 cm for compressed pellets | 4-5 · Results and Discussion · Figures 5-6 |
| Br0.22@Cu[Cu(pdt)2]research_0718__mat__mat_br_cu_cu_pdt2 | Powder · Target Sample · Doped | Elemental-analysis and Le Bail sample with x = 0.22.none | S3 · Table S1/S2 · Table S1; Table S2 |
| Br0.30@Cu[Cu(pdt)2]research_0718__mat__mat_br_cu_cu_pdt2 | Powder · Target Sample · Doped | Optical spectroscopy figure sample labelled x = 0.30.none | 4-5 · Results and Discussion · Figures 5-6 |
| Br0.38@Cu[Cu(pdt)2]research_0718__mat__mat_br_cu_cu_pdt2 | Powder · Target Sample · Doped | Le Bail sample with x = 0.38.none | S3 · Table S1/S2 · Table S1; Table S2 |
| Br0.44@Cu[Cu(pdt)2]research_0718__mat__mat_br_cu_cu_pdt2 | Pellet · Target Sample · Doped | Doped sample used in PXRD, elemental analysis, optical/electrical/thermoelectric figures, and temperature-dependent conductivity.none · typically 0.05 cm for compressed pellets | 4-5 · Results and Discussion · Figures 5-6 |
| Br0.62@Cu[Cu(pdt)2]research_0718__mat__mat_br_cu_cu_pdt2 | Pellet · Target Sample · Doped | Doped sample used in PXRD, elemental analysis, electrical conductivity and thermoelectric figures.none · typically 0.05 cm for compressed pellets | 4-5 · Results and Discussion · Figures 5-6 |
| Br0.94@Cu[Cu(pdt)2]research_0718__mat__mat_br_cu_cu_pdt2 | Pellet · Target Sample · Doped | Highest tabulated doping sample used in PXRD, elemental analysis, electrical conductivity and thermoelectric figures.none · typically 0.05 cm for compressed pellets | 4-5 · Results and Discussion · Figures 5-6 |
| Brx@Cu[Cu(pdt)2] bromine-doped seriesresearch_0718__mat__mat_br_cu_cu_pdt2 | Powder · Target Sample · Doped | Series prepared by varying injected bromine-vapour volume while holding MOF amount constant.none | 2 · Bromine Vapor Doping |
| [Cu(pdt)2] model speciesresearch_0718__mat__mat_cupdt2_model_species | Model · Model System · Model | Isolated [CuII(pdt)2]2- and [CuIII(pdt)2]- species for DFT and redox discussion.none | 3 · Results and Discussion · Figure 2c; Figure 3 |
| Cu[Cu(pdt)2] pristineresearch_0718__mat__mat_cu_cu_pdt2 | Powder · Pristine Control · Pristine Framework | Black polycrystalline solid; used as powder and as compressed pellets for transport/thermoelectric tests.none | 2 · Synthesis of Cu[Cu(pdt)2] |
| Cu[Cu(pdt)2] single crystal for in situ Br2 exposureresearch_0718__mat__mat_cu_cu_pdt2 | Single Crystal · Target Sample · Pristine Framework | Single crystal exposed to Br2 vapour during resistance time-course measurement; becomes bromine-doped during the experiment.none | S6 · Supporting Information · Figure S5 |