Zhou H.-Q., He Y., Hu J.-Y. et al. · Chemical Communications · 2021 · 187-190
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Paraphrased for this database from the authors’ stated interpretations — never quoted verbatim — and kept separate from reported measurements.
FeCl3 oxidative homocoupling of pendant thiophene arms creates conjugated covalent crosslinks that raise electronic conductivity of ZrBPD-4F4TS-Ox relative to ZrBPD-4F4TS.
Caveat: Electronic conductivity measured by a simple two-probe pellet/multimeter setup; contact resistance may contribute.
PDF p.4-PDF p.5 / article p.189-190 · Main text · Table S2; Fig. S37; Fig. S40 · Linked to 4 structured results
The crosslinked ZrBPD-4F4TS-Ox framework retains crystalline order and morphology under air, acid and base conditions where pristine ZrBPD-4F4TS degrades or dissolves.
Caveat: Under harsher 0.2% HF/1.8% HCl treatment the remaining ZrBPD-4F4TS-Ox-derived solid becomes amorphous after Zr extraction.
PDF p.3-PDF p.4 / article p.188-189 · Main text · Fig. 2; Fig. S14-S17 · Linked to 3 structured results
N2-accessible surface area collapses after crosslinking because rigidified crosslinked thiophene units block N2 entry, while smaller/quadrupolar CO2 still accesses pores substantially.
Caveat: This is the authors' interpretation based on sorption contrasts rather than direct pore visualisation.
PDF p.4 / article p.189 · Main text · Fig. S33-S36 · Linked to 4 structured results
The oxidative crosslinking reaction appears controlled by FeCl3 diffusion from the crystallite surface to the core; deficient FeCl3 gives incomplete polymerisation and lower conductivity.
Caveat: Mechanistic inference from NMR/PXRD and conductivity comparisons; no direct diffusion measurement reported.
PDF p.4-PDF p.5 / article p.189-190 · Main text · Fig. S20-S21; Fig. S41 · Linked to 1 structured result
Treating acid-stable ZrBPD-4F4TS-Ox with 1 M H2SO4 increases proton conductivity by several thousand-fold relative to the untreated crosslinked framework.
Caveat: H2SO4 loading amount is not reported; table values are at 90% RH and elevated temperature.
PDF p.4 / article p.189 · Main text · Fig. 3; Table S3 · Linked to 3 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| CH3BPD-4F4TS | C32H18F4O4S8none · Dimethyl 2,2',5,5'-tetrafluoro-3,3',6,6'-tetrakis(thiophenethiol)-[1,1'-biphenyl]-4,4'-dicarboxylate | 0D · Model SystemMolecular methyl ester precursor; monoclinic P21/c single-crystal structure, CCDC 2026236. | CIF text · data_CH3BPD-4F4TS · CCDC 2026236 |
| H2BPD-4F4TS | C30H14F4O4S8none · 2,2',5,5'-tetrafluoro-3,3',6,6'-tetrakis(2-thiophenethio)-4,4'-biphenyl dicarboxylic acid | 0D · Model SystemOrganic linker precursor for the Zr framework; characterised by 1H, 19F and 13C NMR and FT-IR. | PDF p.3 / article p.188 · Main text · Fig. 1; Fig. S1 |
| H2BPD-4F4TS-p | solution-polymerised H2BPD-4F4TS product; empirical formula not reportednone · FeCl3-polymerised H2BPD-4F4TS organic network | unknown · Model SystemNon-MOF polymer comparison material for optical/FT-IR comparison with ZrBPD-4F4TS-Ox. | SI p.S13 · MOF syntheses · Solution polymerization |
| H2SO4@ZrBPD-4F4TS-Ox | H2SO4-treated ZrBPD-4F4TS-Ox; loading amount not reportedZr6-carboxylate host net inherited from ZrBPD-4F4TS-Ox · Conjugated crosslinked BPD-4F4TS linkers with sulfuric-acid-treated proton-conducting state | 3D · PristineAcid-treated crosslinked framework used for high proton-conductivity Nyquist plots. | SI p.S14 · MOF syntheses · Preparation of H2SO4@ZrBPD-4F4TS-Ox |
| ZrBPD-4F4TS | Zr6O4(OH)4(C30H12F4O4S8)3.8(HCOO)4.4(H2O)6Zr6O4(OH)4(CO2)12 clusters in a face-centred cubic array · BPD-4F4TS carboxylate linkers bearing pendant thiophenethio groups; linker deficient with formate terminal donors by elemental analysis | 3D · PristineUiO-67-type fcu framework; partially resolved F-43m model with unresolved/disordered pendant thiophene and F groups. | SI p.S11 · MOF syntheses · Self-assembly synthesis |
| ZrBPD-4F4TS-Ox | FeCl3-oxidised/crosslinked derivative of ZrBPD-4F4TS; exact post-oxidation framework formula not resolvedRetained Zr6-carboxylate host net after oxidative crosslinking · BPD-4F4TS linkers with FeCl3-homocoupled thiophene units forming conjugated C-C crosslinks through sulfide-linked thiophene arms | 3D · PristineCrosslinked UiO-67-type host net; SCXRD differences from ZrBPD-4F4TS not resolved, but PXRD confirms retained crystalline order under multiple tests. | PDF p.3 / article p.188 · Main text · Fig. 1; Fig. 2 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| CH3BPD-4F4TS single crystalresearch_0254__mat__mat_ch3bpd_4f4ts | Single Crystal · Model System · Model | Molecular precursor crystal used for SCXRD/CIF deposition. | CIF text · experimental crystal data · CIF |
| H2BPD-4F4TS linker powderresearch_0254__mat__mat_h2bpd_4f4ts | Powder · Model System · Model | Dicarboxylic-acid linker isolated by precipitation and dried for solvothermal synthesis without further purification. | SI p.S10 · Synthesis of H2BPD-4F4TS · Fig. S1 |
| H2BPD-4F4TS-p yellow polymer productresearch_0254__mat__mat_h2bpd_4f4ts_p | Powder · Model System · Model | Solution-polymerised H2BPD-4F4TS using FeCl3 in dichloromethane. | SI p.S13 · Solution polymerization · Fig. S38-S39 |
| H2SO4@ZrBPD-4F4TS-Oxresearch_0254__mat__mat_h2so4_zrbpd_4f4ts_ox | Powder · Target Sample · Guest Loaded | As-made ZrBPD-4F4TS-Ox stirred in 1 M H2SO4 aqueous solution for 1 h, centrifuged and dried at 60 deg C for 2 h. | SI p.S14 · Preparation of H2SO4@ZrBPD-4F4TS-Ox · Fig. 3; Fig. S28-S29; Table S3 |
| activated ZrBPD-4F4TSresearch_0254__mat__mat_zrbpd_4f4ts | Powder · Pristine Control · Pristine Framework | As-made crystals Soxhlet-extracted in acetone for 3 days and heated at 120 deg C under vacuum. | SI p.S12 · Activation of ZrBPD-4F4TS · Fig. S32-S37; Table S2-S3 |
| as-made ZrBPD-4F4TS colourless octahedron-shaped crystalsresearch_0254__mat__mat_zrbpd_4f4ts | Single Crystal · Pristine Control · Pristine Framework | Solvothermal as-made crystals, DMF-soaked/washed after synthesis. | SI p.S11 · Self-assembly synthesis · Fig. S9 |
| ZrBPD-4F4TS oxidised with deficient FeCl3research_0254__mat__mat_zrbpd_4f4ts_ox | Powder · Target Sample · Doped | Oxidised with 0.5:1 FeCl3/thiophene for incomplete polymerisation; exact standalone recipe not otherwise given. | PDF p.5 / article p.190 · Main text · Fig. S20-S21; Fig. S41 |
| activated ZrBPD-4F4TS-Oxresearch_0254__mat__mat_zrbpd_4f4ts_ox | Powder · Target Sample · Doped | As-made ZrBPD-4F4TS-Ox Soxhlet-extracted in methanol for 3 days and heated at 120 deg C under vacuum. | SI p.S12 · Activation of ZrBPD-4F4TS-Ox · Fig. 2f; Fig. S25-S37 |
| as-made ZrBPD-4F4TS-Ox brown powderresearch_0254__mat__mat_zrbpd_4f4ts_ox | Powder · Target Sample · Doped | Activated ZrBPD-4F4TS treated with excess FeCl3 in nitromethane/toluene at 90 deg C for 120 h, washed and dried in air. | SI p.S12 · Preparation of ZrBPD-4F4TS-Ox · Fig. 1; Fig. 2 |