Yan M., Bowman Z., Knepp Z.J. et al. · Journal of Physical Chemistry Letters · 2024 · 11919-11926
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.
Introducing conjugated redox-active complexes capable of radical-cation character could enhance hole transfer during electrochemical oxidation and yield p-type semiconductor-like MOF behaviour.
Caveat: Forward-looking design suggestion; not experimentally tested in this paper.
p007 / article page 11925 · Conclusion
Because ion diffusion is often rate-determining in redox-hopping systems, Ru-NU-1000 is proposed to be better suited to reductive electrocatalysis.
Caveat: The paper studies charge transport, not a catalytic performance metric for a specific reaction.
p006 / article page 11924 · Results and discussion · Linked to 3 structured results
The unexpectedly faster reduction is attributed primarily to shorter effective redox-site spacing and delocalised bpy-centred electron density, rather than to molecular self-exchange rates.
Caveat: Mechanistic interpretation combines experimental transport with DFT and structural-distance modelling.
p006-p007 / article pages 11924-11925 · Results and discussion · Linked to 4 structured results
Ion diffusion is faster during reduction because anions deintercalate through a more open path, whereas oxidation requires additional anions to diffuse into more crowded channels or break ion pairs.
Caveat: Ion-motion explanation is mechanistic interpretation rather than a directly imaged ion pathway.
p006 / article page 11924 · Results and discussion · Linked to 2 structured results
Ru-NU-1000 exhibits faster reductive charge transport than oxidative charge transport in both surface and bulk redox-hopping regimes.
Caveat: Stage A Di values are within error; main prose contains one swapped-label sentence, so Table 1 is used as authoritative.
p006 / article page 11924 · Conclusion · Linked to 6 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| NU-1000 | Zr-based NU-1000 MOF; molar mass used in SI model = 2180 g/molZr oxo-metal nodes · 1,3,6,8-tetrakis(p-benzoate)pyrene (H4TBAPy/TBAPy) | 3D · PristinePorous NU-1000 scaffold with hexagonal tunnels; PXRD of NU-1000 and Ru-NU-1000 compared with simulated NU-1000. | p002 / article page 11920 · Results and discussion · Figure 2 |
| [RuII(bpy)2(bpy-COOH)](PF6)2 | [RuII(bpy)2(bpy-COOH)](PF6)2molecular Ru(II) centre, not a MOF node · 2,2'-bipyridine and 4-carboxy-2,2'-bipyridine ligands | 0D · Model SystemMolecular redox centre used as SALI reagent, homogeneous electrochemical control, and DFT model. | p001 · Synthesis of [RuII(bpy)2(bpy-COOH)](PF6)2 |
| Ru-NU-1000 | NU-1000 with anchored [RuII(bpy)2(bpy-COOH)]2+ redox centresZr oxo-metal nodes bearing anchored Ru polypyridyl centres · NU-1000 TBAPy linkers plus bpy/bpy-COOH ligands on Ru complex | 3D · Pristine[RuII(bpy)2(bpy-COOH)]2+ centres anchored on NU-1000 nodes by SALI; NMR loading indicates approximately one Ru complex per Zr node. | p002 / article page 11920 · Results and discussion |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| NU-1000 particlesresearch_0321__mat__mat_nu1000 | Powder · Pristine Control · Pristine Framework | Solvothermal NU-1000 powder; acid washed, solvent washed, and vacuum dried. | p001 · Synthesis of NU-1000 |
| Pristine NU-1000 electrochemical control on FTOresearch_0321__mat__mat_nu1000 | Electrode · Pristine Control · Pristine Framework | Pristine NU-1000 film/control compared with Ru-NU-1000 and blank FTO by CV/DPV.FTO · not reported | p005 · Electrochemical measurements · Figure S7 |
| [Ru(bpy)2(bpy-COOH)] charge-state DFT modelsresearch_0321__mat__mat_ru_complex_model | Model · Model System · Model | Reduced 1+, neutral/parent 2+, and oxidized 3+ molecular structures with and without MeCN PCM. | p006-p008 · Density Functional Theory · Tables S1-S2; Figures S9-S11 |
| [RuII(bpy)2(bpy-COOH)](PF6)2 homogeneous solutionresearch_0321__mat__mat_ru_complex_model | Model · Model System · Model | Molecular Ru complex dissolved in acetonitrile/TBAPF6 for homogeneous electrochemical comparison.glassy carbon electrode for solution CV | p004 · Electrochemical measurements · Figure S6 |
| Ru-NU-1000 film on FTOresearch_0321__mat__mat_ru_nu1000 | Electrode · Target Sample · Guest Loaded | Ru-NU-1000 particles deposited on FTO by electrophoretic deposition.fluorine-doped tin oxide (FTO) · near particle-thick film | p003 / article page 11921 · Results and discussion · Figure 2 |
| Ru-NU-1000 particlesresearch_0321__mat__mat_ru_nu1000 | Powder · Target Sample · Guest Loaded | NU-1000 particles postsynthetically modified by SALI with [RuII(bpy)2(bpy-COOH)](PF6)2. | p002 · Solvent-assistant ligand incorporation (SALI) of NU-1000 |
| Ru-NU-1000 hopping-distance structural modelresearch_0321__mat__mat_ru_nu1000 | Model · Model System · Model | Uniformly distributed Ru centres in NU-1000 hexagonal tunnels. | p006 / article page 11924 · Results and discussion · Figure 6 |