Pattengale B., Neu J., Tada A. et al. · Polyhedron · 2021 · 115182
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 work suggests cation-functionalised Mn2DSBDC as a tunable platform for potential electrocatalytic or photocatalytic applications without hindering charge transport.
Caveat: No electrochemical application performance measurements are reported in this paper.
8 · 4 Conclusions · Linked to 3 structured results
Post-synthetic cation exchange with Co2+, Cu2+ or Ni2+ retains the overall Mn2DSBDC crystalline framework, although Co and Cu analogues show reduced pXRD intensity near the maximum tolerated exchange loading.
Caveat: Crystallinity loss is noted as exchange percentage approaches about 10 at%.
5 · 3.1 Structure, synthesis, and characterization · Fig. 2 · Linked to 3 structured results
Co, Cu and Ni cation exchange decreases the Tauc x-intercept bandgap from 2.43 eV for pristine Mn2DSBDC to 2.34, 2.14 and 2.05 eV, respectively.
Caveat: Bandgaps exclude the weak exchanged-cation absorption in the 500-700 nm range.
S6 · Supplementary Tables · Table S2 · Linked to 4 structured results
Cation exchange contracts the bulk and local coordination structure relative to pristine Mn2DSBDC, with Mn-Mn distances shortened by about 0.1 Å and exchanged-metal M-O/M-S distances at least about 0.1 Å shorter than corresponding Mn distances.
Caveat: EXAFS fits use fixed coordination numbers and report approximately 0.02 Å uncertainty in R.
6-7 · 3.2 X-ray absorption spectroscopy · Table 1; Table 2 · Linked to 5 structured results
Cation exchange does not significantly disrupt THz AC conductivity; pristine and ca. 8-10 at% Co/Cu/Ni-exchanged Mn2DSBDC show similar conductivities and no observable temperature dependence from 100 to 300 K.
Caveat: Reported conductivity is spectroscopic AC THz conductivity; authors caution it should not be equated directly with probe-based DC conductivity.
7-8 · 3.3; 4 Conclusions · Fig. 6; Figs. S5-S8 · Linked to 4 structured results
Drude-Smith c parameters near -1 imply that mobile carriers are mainly limited by defects or grain boundaries, giving metal-like temperature-insensitive conductivity.
Caveat: Mechanistic interpretation is model-based and the authors leave charge-pathway alternatives open.
7-8 · 3.3 Time domain THz spectroscopy · 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 |
|---|---|---|---|
| Co@Mn2DSBDCBrowse family: Mn₂(DSBDC) | Co-exchanged Mn2DSBDC, ca. 10.2 at% Co with respect to Mn by XRFMostly Mn2+ nodes with partial Co2+ substitution · DSBDC = 2,5-dimercaptoterephthalate | 3D · PristineCation-exchanged analogue retaining the Mn2DSBDC crystal structure by pXRD; local Co environment modelled as octahedral O/S coordination. | 3 · 3.1 Structure, synthesis, and characterization · Fig. 2; Table S1 |
| Cu@Mn2DSBDCBrowse family: Mn₂(DSBDC) | Cu-exchanged Mn2DSBDC, ca. 8.2 at% Cu with respect to Mn by XRFMostly Mn2+ nodes with partial Cu2+ substitution · DSBDC = 2,5-dimercaptoterephthalate | 3D · PristineCation-exchanged analogue retaining the Mn2DSBDC crystal structure by pXRD; Cu assigned to S-coordinated sites from XANES. | 5 · 3.2 X-ray absorption spectroscopy · Fig. 4 |
| 2,5-dimercaptoterephthalic acid (H2DSBDC) | H2DSBDCnone · MOF linker precursor, deprotonated as DSBDC in Mn2DSBDC | 0D · UnknownMolecular organic linker used to prepare Mn2DSBDC. | 2 · 2.4 Synthesis of H2DSBDC · Fig. S1 |
| Mn2DSBDCBrowse family: Mn₂(DSBDC) | Mn2(2,5-dimercaptoterephthalate); reported as Mn2DSBDCMn2+ centres in continuous alternating Mn1/Mn2 chains · DSBDC = 2,5-dimercaptoterephthalate | 3D · PristineMicroporous MOF with hexagonal pores and continuous Mn-S-Mn-S chains; as-prepared material has DMF coordinated to Mn2 sites. | 3 · 3.1 Structure, synthesis, and characterization · Fig. 1 |
| Ni@Mn2DSBDCBrowse family: Mn₂(DSBDC) | Ni-exchanged Mn2DSBDC, ca. 7.5 at% Ni with respect to Mn by XRFMostly Mn2+ nodes with partial Ni2+ substitution · DSBDC = 2,5-dimercaptoterephthalate | 3D · PristineCation-exchanged analogue retaining the Mn2DSBDC crystal structure by pXRD; Ni local environment modelled as octahedral O/S coordination with a second-shell Ni-X feature. | 6 · 3.2 X-ray absorption spectroscopy · Fig. 5; Table 2 |
| diethyl 2,5-bis((dimethylcarbamothioyl)oxy)terephthalate (S2) | organic ligand precursor S2none · terephthalate derivative precursor to H2DSBDC | 0D · UnknownMolecular precursor in linker synthesis. | 2 · 2.2 Synthesis of S2 · Fig. S1 |
| diethyl 2,5-bis((dimethylcarbamoyl)thio)terephthalate (S3) | organic ligand precursor S3none · terephthalate derivative precursor to H2DSBDC | 0D · UnknownMolecular precursor in linker synthesis. | 2 · 2.3 Synthesis of S3 · Fig. S1 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| Co@Mn2DSBDC powderresearch_0894__mat__mat_co_mn2dsbdc | Powder · Target Sample · Mixed Metal | Post-synthetic Co2+ exchanged powder; dried under ambient conditions; pelletised with PTFE for THz-TDS. | S6 · Supplementary Tables · Table S1 |
| Cu@Mn2DSBDC powderresearch_0894__mat__mat_cu_mn2dsbdc | Powder · Target Sample · Mixed Metal | Post-synthetic Cu2+ exchanged powder; dried under ambient conditions; pelletised with PTFE for THz-TDS. | S6 · Supplementary Tables · Table S1 |
| H2DSBDC linker solidresearch_0894__mat__mat_h2dsbdc_linker | Powder · Paper Level Unspecified · Unknown | Yellow solid ligand isolated after basic hydrolysis, acid precipitation, washing and high-vacuum drying. | 2 · 2.4 Synthesis of H2DSBDC |
| as-prepared Mn2DSBDC powderresearch_0894__mat__mat_mn2dsbdc | Powder · Pristine Control · Pristine Framework | As-prepared air-stable solid; DMF-coordinated material investigated; pelletised with PTFE for THz-TDS. | 2 · 2.5 Synthesis of Mn2DSBDC MOF |
| Ni@Mn2DSBDC powderresearch_0894__mat__mat_ni_mn2dsbdc | Powder · Target Sample · Mixed Metal | Post-synthetic Ni2+ exchanged powder; dried under ambient conditions; pelletised with PTFE for THz-TDS. | S6 · Supplementary Tables · Table S1 |
| S2 precursor solidresearch_0894__mat__mat_s2_precursor | Powder · Paper Level Unspecified · Unknown | White solid precursor isolated by filtration and high-vacuum drying. | 2 · 2.2 Synthesis of S2 |
| S3 precursor solidresearch_0894__mat__mat_s3_precursor | Powder · Paper Level Unspecified · Unknown | Pale brown solid precursor isolated after thermal rearrangement, ethanol addition, centrifugation, and high-vacuum drying. | 2 · 2.3 Synthesis of S3 |