Tominaka S., Hamoudi H., Suga T. et al. · Chemical Science · 2015 · 1465-1473
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 crystalline insulating dense MOF [CuICl(ttcH3)] is converted into an amorphous MOF semiconductor [CuI1.8(ttcH1.2)].
Caveat: Conductivity remains modest despite the narrow optical gap.
8 · Conclusions · Linked to 4 structured results
Conductivity in compound 3 is attributed to an inorganic CuSx/Cu-S-Cu network rather than direct Cu-Cu metal-to-metal conduction.
Caveat: The approximately 3.2 A Cu-Cu distance comes from broad PDF features and is explicitly described as less definitive than sharp-peak distances.
6 · Atomic structure · Figure 6 · Linked to 4 structured results
Ammonia solution at pH 11.4 is essential for dechlorination; lower pH gives incomplete dechlorination and higher pH dissolves compound 1.
Caveat: The paper reports the comparative outcome but does not give full recipes for failed lower- or higher-pH trials.
7 · Outline of the conversion reactions · Linked to 2 structured results
Compound 1 converts topochemically to compound 2 and then compound 3, with the reaction proceeding from the surface inward while retaining crystal morphology.
Caveat: Mechanistic description is inferred from time-dependent diffraction/appearance and chemical reasoning.
7 · Outline of the conversion reactions · Figure S13 · Linked to 2 structured results
Additional unoccupied S-derived states in compound 3 near the Fermi level account for the colour change, narrowed optical gap, and semiconducting behaviour.
Caveat: The authors call the DFT treatment preliminary, especially for the full amorphous system.
7 · Electronic states · Figure 7 and Figure S14 · Linked to 3 structured results
Temperature-dependent conductivity in compound 3 is consistent with hopping or thermal activation rather than tunnelling, but variable-range-hopping dimensionality fits are inconclusive.
Caveat: The SI plots can be fitted to multiple dimensionalities, so the precise conduction pathway is not uniquely established.
3 · Conductivity measurements · Figure S7 · Linked to 2 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| Compound 1, copper(I) chloride trithiocyanurate | CuICl(ttcH3); C3H3ClCuN3S3Cu(I) · trithiocyanuric acid (ttcH3) | 3D · PristineDense crystalline MOF; CuClS3 tetrahedra connected by neutral ttcH3 molecules; Pa-3 cubic structure. | 1 · Abstract/Introduction · Figure 1 |
| Compound 2, ammonia-treated Cu-trithiocyanurate intermediate | (H3O)0.7(NH4)0.5[Cu1.8(ttc)]Cu(I) · deprotonated trithiocyanurate (ttc) | unknown · PristineAmorphous to X-rays with diffuse scattering and weak peaks; hydrated/ammoniated intermediate after aqueous ammonia treatment. | 3 · Appearance & composition · Figure 2 |
| Compound 3, amorphous copper trithiocyanurate semiconductor | CuI1.8(ttc)0.6(ttcH3)0.4; Cu1.8(C3N3S3H1.2)Cu(I) · partially deprotonated trithiocyanurate, (ttc3-)0.6(ttcH3)0.4 | 3D · PristineAmorphous MOF with chemical short-range order and inferred inorganic Cu-S-Cu network; dimensionality described as IxO3-x (x > 1). | 1 · Abstract |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| Compound 1 reddish-orange octahedral crystalsresearch_0748__mat__mat_1_cucl_ttcH3 | Single Crystal · Pristine Control · Pristine Framework | Solvothermally grown, vacuum-filtered and ethanol-rinsed crystals. | 2 · Experimental - Synthesis |
| Compound 1 powder pelletresearch_0748__mat__mat_1_cucl_ttcH3 | Pellet · Pristine Control · Pristine Framework | Ground powder pelletised at 0.5 GPa with a few drops of water, then dried under vacuum.ca. 0.6 mm | 3 · Conductivity measurements |
| Compound 2 ammonia-treated monolithresearch_0748__mat__mat_2_ammonia_intermediate | Unknown · Target Sample · Guest Loaded | Compound 1 crystals treated in 0.43% aqueous ammonia for 2 days and rinsed with distilled water. | 2 · Experimental - Synthesis · Figure 2 |
| Compound 3, 5-day ammonia-treatment replicateresearch_0748__mat__mat_3_amorphous_cu_ttc | Pellet · Target Sample · Pristine Framework | Compound 1 treated in aqueous ammonia for 5 days, then dried under vacuum. | 2 · Experimental - Synthesis |
| Compound 3 vacuum-dried black monolithresearch_0748__mat__mat_3_amorphous_cu_ttc | Unknown · Target Sample · Pristine Framework | Compound 2 dried at 130 deg C under vacuum for more than 6 h. | 2 · Experimental - Synthesis · Figure 2 |
| Compound 3 powder pelletresearch_0748__mat__mat_3_amorphous_cu_ttc | Pellet · Target Sample · Pristine Framework | Gently ground, pelletised at 0.5 GPa with a few drops of water, dried at 130 deg C under vacuum overnight, then measured under nitrogen.ca. 0.6 mm | 3 · Conductivity measurements · Figure 3 |
| Compound 3 single monolith on microelectrodesresearch_0748__mat__mat_3_amorphous_cu_ttc | Single Crystal · Target Sample · Pristine Framework | Single monolith mounted on microelectrodes for impedance screening.quartz chip with Au microelectrodes · edge length ca. 130 um; electrode gap 80 um | S6 · Additional AC impedance data · Figure S5 |
| Computational model of compound 1research_0748__mat__mat_1_cucl_ttcH3 | Model · Model System · Model | Crystalline system model for DFT. | S15 · DFT calculations · Figure S14 |
| Computational local model of compound 3research_0748__mat__mat_3_amorphous_cu_ttc | Model · Model System · Model | Locally ordered PDF-refined model for DFT. | S15 · DFT calculations · Figure S14 |