Chong S., Kim J. · Dalton Transactions · 2019 · 102-113
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.
Chemical reduction of x/y-axial DHBQ linkers is predicted to lower the linker-saturated Ce-PCN-700-DHBQ bandgap from 2.09 eV to 1.25 eV, suggesting tunability for chemiresistive sensing.
Caveat: Application relevance is inferred from computed bandgap tuning; no sensing device or response measurement is reported.
main p.10, article p.111 · Conclusion · Linked to 2 structured results
This is a computational study and reports no first-hand experimental synthesis route for the modified PCN-700 materials.
Caveat: The text discusses possible immersion/high-concentration linker installation and cites prior experimental PCN-700 linker-installation work, but those are not first-hand synthesis recipes in this paper.
main p.1, article p.102 · Abstract
Computations predict that DHBQ can coordinate in a 1:1 mode at both ends and bridge PCN-700 metal clusters, supporting sequential linker installation at z-axial sites.
Caveat: This is a computational feasibility claim, not an experimental synthesis demonstration.
main p.5, article p.106 · Sequential linker installation of DHBQ in PCN-700 · Fig. 3; Fig. S1; Fig. S2 · Linked to 3 structured results
Ce substitution improves metal-linker energy-level matching in PCN-700-DHBQ, but cluster oxygen states remain insufficient, preventing long-range CT without further linker saturation.
Caveat: The paper notes experimental synthesis of metal-substituted PCN-700 had not been reported.
main p.8, article p.109 · Metal substitution · Fig. 5; Fig. 6; Fig. S4 · Linked to 4 structured results
Linker-saturated Ce-PCN-700-DHBQ is predicted to exhibit semiconducting behaviour and continuous charge-transport pathways through Ce ions and DHBQ linkers upon excitation.
Caveat: No experimental electrical conductivity, mobility, Seebeck coefficient, or carrier density was measured.
main p.9, article p.110 · Linker saturation · Fig. 8 · Linked to 5 structured results
DHBQ installation in Zr-PCN-700 reduces the bandgap but leaves frontier orbitals localised on DHBQ, so the proposed through-bond CT pathway is not continuous.
Caveat: Transport mechanism inferred from DOS/PDOS/orbital composition only.
main p.6, article p.107 · Electronic properties of PCN-700-DHBQ · Fig. 5a; Fig. 6 · Linked to 3 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| Ce-PCN-700-DHBQ computational model | Not specifiedCe-substituted PCN-700 metal clusters, replacing Zr4+ with Ce4+ in the model · PCN-700 framework with DHBQ linkers at z-axial vacant sites | 3D · Model SystemGeometry-optimised Ce-substituted PCN-700-DHBQ model; Ce 4f band overlaps DHBQ-derived LUCO. | main p.7, article p.108 · Metal substitution · Fig. 5 and Fig. 6 |
| Linker saturated Ce-PCN-700-DHBQ computational model | Not specifiedCe-substituted PCN-700 metal clusters · DHBQ at z-axial and additional x/y-axial linker vacant sites | 3D · Model SystemDFT-relaxed Ce-PCN-700-DHBQ with DHBQ saturated at all available linker vacant sites; additional x/y-axial DHBQ linkers serve as detouring CT paths. | main p.8, article p.109 · Linker saturation · Fig. 7 |
| PCN-700-BDC computational reference model | Not specifiedZr6O4(OH)4 zirconium-oxo clusters · PCN-700 framework with BDC installed in z-axial linker positions | 3D · Model SystemDFT-optimised reference linker-installed PCN-700 structure. | main p.5, article p.106 · Electronic properties of PCN-700-DHBQ · Table 1; Fig. S3 |
| PCN-700-DHBQ computational model | Not specifiedZr6O4(OH)4 zirconium-oxo clusters · Original PCN-700 linkers plus 2,5-dihydroxybenzoquinone (DHBQ) linkers coordinated at z-axial vacant sites | 3D · Model SystemDFT-relaxed periodic PCN-700 model with DHBQ fully coordinated at z-axial linker vacant sites; remaining x/y-axial vacant sites modelled with water and hydroxyl groups. | main p.6, article p.107 · Electronic properties of PCN-700-DHBQ · Fig. 4 |
| PCN-700 linker-installation model series | Not specifiedZr6O4(OH)4 PCN-700 clusters · FA, DHBQ, BDC, NDC, or BPDC installed in PCN-700 in separate MD models | 3D · Model SystemFlexible MD models used to validate sequential linker installation and unit-cell dimensions. | main p.5, article p.106 · Electronic properties of PCN-700-DHBQ · Table 1 |
| PCN-700 computational model | Not specifiedZr6O4(OH)4 zirconium-oxo clusters · Methylated biphenyldicarboxylate (Me2-BPDC) linkers in the PCN-700 framework; vacant linker sites modulated by water/hydroxyl in DOS models. | 3D · Model SystemZirconium MOF with 8-connected bcu topology, undercoordinated relative to 12-connected UiO-67 due to methyl-BPDC torsion. | main p.2, article p.103 · Introduction · Fig. 1 |
| Reduced linker saturated Ce-PCN-700-DHBQ computational model | Not specifiedCe-substituted PCN-700 metal clusters · DHBQ at all available linker vacant sites, with x/y-axial DHBQ linkers expressed as dianions | 3D · Model SystemGeometry-optimised reduced x/y-axial DHBQ variant of linker saturated Ce-PCN-700-DHBQ. | main p.10, article p.111 · Linker saturation · Fig. S5 |
| Ti-PCN-700-DHBQ computational model | Not specifiedTi-substituted PCN-700 metal clusters, replacing Zr4+ with Ti4+ in the model · PCN-700 framework with DHBQ linkers at z-axial vacant sites | 3D · Model SystemGeometry-optimised metal-substituted M-PCN-700-DHBQ model. | main p.7, article p.108 · Metal substitution · Fig. 5 |
| DHBQ coordinated Zr6O4(OH)4 cluster model | Zr6O4(OH)4 cluster with formate modulators and DHBQ linker(s)Zr6O4(OH)4 cluster models · DHBQ and formate modulators | 0D · Model SystemFinite cluster DFT model used to analyse DHBQ coordination modes rather than a periodic MOF. | main p.3, article p.104 · DHBQ coordination mode analysis |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| DFT Ce-PCN-700-DHBQ modelresearch_0143__mat__ce_pcn700_dhbq_model | Model · Model System · Model | Geometry-optimised metal-substituted model followed by PDOS and orbital-density analysis.not_applicable · not_applicable | main p.7, article p.108 · Metal substitution · Fig. 5c |
| DFT linker saturated Ce-PCN-700-DHBQ modelresearch_0143__mat__linker_saturated_ce_pcn700_dhbq_model | Model · Target Sample · Model | Geometry optimised and PDOS analysed after saturating all available linker vacant sites with DHBQ.not_applicable · not_applicable | main p.8, article p.109 · Linker saturation · Fig. 7 |
| DFT PCN-700-BDC reference modelresearch_0143__mat__pcn700_bdc_model | Model · Model System · Model | Optimised reference structure with BDC linker installation.not_applicable · not_applicable | SI p.6 · Supporting information · Fig. S3 |
| DFT PCN-700-DHBQ model with z-axial DHBQresearch_0143__mat__pcn700_dhbq_model | Model · Model System · Model | Geometry optimised; DHBQ assumed fully coordinated at all z-axial vacant sites.not_applicable · not_applicable | main p.5, article p.106 · Electronic properties of PCN-700-DHBQ · Fig. 4 |
| Flexible MD PCN-700 linker-installation seriesresearch_0143__mat__pcn700_linker_installation_series_model | Model · Model System · Model | LAMMPS flexible MD simulations with unbound linkers positioned laterally between z-axial metal clusters.not_applicable · not_applicable | main p.5, article p.106 · Electronic properties of PCN-700-DHBQ · Table 1 |
| DFT PCN-700 reference modelresearch_0143__mat__pcn700_model | Model · Model System · Model | All-atomic periodic DFT model; water/hydroxyl groups coordinated at linker vacant sites in DOS calculations.not_applicable · not_applicable | main p.5, article p.106 · Electronic properties of PCN-700-DHBQ · Fig. 4 |
| DFT reduced x/y-DHBQ linker saturated Ce-PCN-700-DHBQ modelresearch_0143__mat__reduced_linker_saturated_ce_pcn700_dhbq_model | Model · Model System · Model | Geometry optimisation and PDOS repeated with x/y-axial DHBQ linkers expressed as dianions.not_applicable · not_applicable | main p.10, article p.111 · Linker saturation · Fig. S5 |
| DFT Ti-PCN-700-DHBQ modelresearch_0143__mat__ti_pcn700_dhbq_model | Model · Model System · Model | Geometry-optimised metal-substituted model followed by PDOS.not_applicable · not_applicable | main p.7, article p.108 · Metal substitution · Fig. 5b |
| Finite Zr6O4(OH)4-DHBQ cluster coordination modelresearch_0143__mat__zr6_dhbq_cluster_model | Model · Model System · Model | Gaussian09 B3LYP cluster-model geometry optimisation and binding-energy calculation.not_applicable · not_applicable | main p.3, article p.104 · DHBQ coordination mode analysis |