Qu L., Iguchi H., Ueno K. et al. · Angewandte Chemie - International Edition · 2026 · e15533
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.
PMC-3-Br supports reversible redox-driven cation insertion into counterion-free pores, making the family relevant to electrode materials and tunable electrochemical ion insertion.
Caveat: Electrochemical evidence is shown for PMC-3-Br as representative; no battery cycling metrics are reported.
main p.6-p.8 · Redox Activity · Figures 6, S11-S14 · Linked to 8 structured results
Although PMC-3 frameworks have large crystallographic void volumes, crystallinity decreases with lattice-solvent loss and measured gas uptake is strongly reduced.
Caveat: Gas sorption is shown for PMC-3-Br; the accessible porosity of fully activated, structurally intact material is not established.
main p.3 · Syntheses and Structures · Figures S5-S6 · Linked to 3 structured results
PMC-3-Cl, PMC-3-Br and PMC-3-I have identical halide counts as coordinating ligands, no counterions in the voids and a constant average NDI-core charge/carrier density of -0.67.
Caveat: Solvent content in PMC-3-Br decreases during drying; framework charge assignment is based on empirical formula and spectroscopy.
main p.3 and p.8 · Syntheses and Structures; Conclusion · Linked to 1 structured result
Non-contact FP-TRMC shows phiSigmaMu increasing from Cl to Br to I, establishing a correlation between shorter c-axis pi-stacking distance/flatter NDI geometry and improved intrinsic charge transport.
Caveat: phiSigmaMu is a product of quantum yield and mobility sum, not a direct mobility alone; FP-TRMC samples include PMMA binder on quartz.
main p.6 · Correlation Between the Lattice Parameter c and Charge Transport Properties · Figure 5; Table S6 · Linked to 5 structured results
Increasing halide ionic radius from Cl to Br to I reduces the c-axis/pi-stacking repeat and acts as negative chemical pressure.
Caveat: The detailed mechanistic explanation relies on crystallographic angle analysis and steric arguments rather than direct force measurements.
main p.5-p.6 · Halide-Dependent Variation in pi-Stacking Geometry · Figure 4; Table 1 · Linked to 5 structured results
Single crystals of PMC-3-Cl and PMC-3-Br show semiconducting c-axis conductivity on the order of 10-3 S cm-1, with the best reported value 5.5 x 10-3 S cm-1 for PMC-3-Br.
Caveat: Two-probe single-crystal values can be affected by contact resistance and cracking; PMC-3-I could not be measured as a single crystal.
main p.4-p.5 · Electrical Conductivity · Figure 3; Tables S3-S4 · Linked to 4 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| NDI-py ligand control | N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxdiimideNone. · Molecular NDI-py ligand precursor and electrochemical/spectroscopic control. | 0D · Model SystemMolecular ligand control, not a MOF. | main p.2 and p.4 · Introduction; Electronic States · Figure 2; Figure S12 |
| PMC-3-Br | Empirical framework/solvate: [Zn(OH2)4(NDI-py)][ZnBr2(NDI-py)]2.8DMA.3H2O; elemental-analysis sample after drying: [Zn(OH2)4(NDI-py)][ZnBr2(NDI-py)]2.6DMA; SQUEEZE crystallographic formula C72H44O16N12Br4Zn3Zn(1) octahedral centres coordinated by four H2O and two NDI-py ligands; Zn(2) tetrahedral centres coordinated by two NDI-py ligands and two bromide ions. · NDI-py ligands with mixed neutral NDI0 and radical anion NDI.- cores. | 3D · PristineOrthorhombic Cmme isostructural PMC-3 framework; representative crystal structure shown with 1D pi-stacked NDI columns and porous packing. | main p.3 · Syntheses and Structures · Figure 1; Table 1 |
| PMC-3-Cl | [Zn(OH2)4(NDI-py)][ZnCl2(NDI-py)]2.8DMA.3H2O; SQUEEZE crystallographic formula C72H44O16N12Cl4Zn3Zn(1) octahedral centres coordinated by four H2O and two NDI-py ligands; Zn(2) tetrahedral centres coordinated by two NDI-py ligands and two chloride ions. · N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxdiimide (NDI-py), with mixed neutral NDI0 and radical anion NDI.- cores. | 3D · PristineOrthorhombic Cmme porous molecular conductor made from interlaced 1D linear and zigzag coordination polymer chains in a 1:2 ratio; NDI cores form 1D pi-stacked columns along the crystallographic c axis. | main p.2-p.3 · Syntheses and Structures · Figure 1; Table 1 |
| PMC-3-I | [Zn(OH2)4(NDI-py)][ZnI2(NDI-py)]2.8DMA.3H2O; SQUEEZE crystallographic formula C72H44O16N12I4Zn3Zn(1) octahedral centres coordinated by four H2O and two NDI-py ligands; Zn(2) tetrahedral centres coordinated by two NDI-py ligands and two iodide ions. · NDI-py ligands with mixed neutral NDI0 and radical anion NDI.- cores. | 3D · PristineOrthorhombic Cmme isostructural PMC-3 framework with shortest c-axis/pi-stacking repeat among the halide series. | main p.5-p.6 · Electrical Conductivity; Halide-Dependent Variation in pi-Stacking Geometry · Figures 4 and 5; Table 1 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| NDI-py ligand control solidresearch_0032__mat__ndi_py | Powder · Pristine Control · Model | Molecular ligand synthesised by a previously reported procedure and used as neutral control.KBr pellet for absorption; glassy carbon electrode for solid-state CV. | SI p.S2 and p.S15 · Experimental details; Figure S12 · Figure S12 |
| PMC-3-Br solid-state electrochemical sampleresearch_0032__mat__pmc3_br | Electrode · Target Sample · Pristine Framework | Solid PMC-3-Br mechanically attached/fixed to electrochemical working electrodes in dry acetonitrile electrolytes under nitrogen or oxygen-free conditions.Glass carbon electrode for CV; ITO glass for UV-vis-NIR SEC; Pt mesh/Pt working electrode for EPR SEC. | SI p.S3-p.S4 · Solid-state cyclic voltammetry; SEC measurements · Figures S11-S14 |
| PMC-3-Br/PMMA drop-cast FP-TRMC sample on quartzresearch_0032__mat__pmc3_br | Thin Film · Target Sample · Composite | Drop-cast with PMMA binder on quartz for FP-TRMC at room temperature in N2.Quartz substrate. | SI p.S4 · FP-TRMC measurement · Figure 5; Table S6 |
| PMC-3-Br pressed pelletsresearch_0032__mat__pmc3_br | Pellet · Target Sample · Pristine Framework | Crystalline samples pressed into pellets for I-V measurement in an N2-purged glovebox.Stainless pellet die assembly with insulating alumina spacer. · 3 mm diameter pressed pellets; thickness measured but not reported. | main p.5 · Electrical Conductivity · Figure S10; Table S5 |
| PMC-3-Br single crystalsresearch_0032__mat__pmc3_br | Single Crystal · Target Sample · Pristine Framework | Dark brown rod-like crystals isolated from cathode, washed with DMA and ethanol, dried under N2; prone to solvent loss/cracking.Pt-Ir cathode during electrocrystallisation; gold wires/carbon paste on PPMS sample pack for conductivity. · Crystal size 0.251 x 0.092 x 0.031 mm in Table S1. | SI p.S2, p.S6 and p.S13 · Synthesis of PMC-3-Br; Table S1; Figure S9 · Table S1; Figure S9 |
| PMC-3-Cl/PMMA drop-cast FP-TRMC sample on quartzresearch_0032__mat__pmc3_cl | Thin Film · Target Sample · Composite | Drop-cast with polymethylmethacrylate binder on quartz for FP-TRMC at room temperature in N2.Quartz substrate. | SI p.S4 · Flash-photolysis time-resolved microwave conductivity measurement · Table S6 |
| PMC-3-Cl pressed pelletsresearch_0032__mat__pmc3_cl | Pellet · Target Sample · Pristine Framework | Crystalline samples pressed into pellets for I-V measurement in an N2-purged glovebox.Stainless pellet die assembly with insulating alumina spacer. · 3 mm diameter pressed pellets; thickness measured but not reported. | SI p.S3 and p.S14 · Electrical conductivity measurement; Table S5 · Figure S10; Table S5 |
| PMC-3-Cl single crystalsresearch_0032__mat__pmc3_cl | Single Crystal · Target Sample · Pristine Framework | Dark brown rectangular-prism/rod-like crystals isolated from the cathode, washed with DMA and ethanol and dried under N2.Pt-Ir cathode during electrocrystallisation; gold wires/carbon paste on PPMS sample pack for conductivity. · Crystal size 0.265 x 0.115 x 0.030 mm in Table S1. | SI p.S2 and p.S6 · Synthesis of PMC-3-Cl; Table S1 · Table S1 |
| PMC-3-I/PMMA drop-cast FP-TRMC sample on quartzresearch_0032__mat__pmc3_i | Thin Film · Target Sample · Composite | Drop-cast with PMMA binder on quartz for FP-TRMC at room temperature in N2.Quartz substrate. | main p.6 · Correlation Between the Lattice Parameter c and Charge Transport Properties · Figure 5; Table S6 |
| PMC-3-I pressed pelletsresearch_0032__mat__pmc3_i | Pellet · Target Sample · Pristine Framework | Crystalline samples pressed into pellets for I-V measurement in an N2-purged glovebox.Stainless pellet die assembly with insulating alumina spacer. · 3 mm diameter pressed pellets; thickness measured but not reported. | main p.5 · Electrical Conductivity · Figure S10; Table S5 |
| PMC-3-I single crystalsresearch_0032__mat__pmc3_i | Single Crystal · Target Sample · Pristine Framework | Dark brown rod-like crystals isolated from cathode, washed with DMA and ethanol, dried under N2.Pt-Ir cathode during electrocrystallisation. · Crystal size 0.331 x 0.060 x 0.025 mm in Table S1. | main p.5 · Electrical Conductivity · Figure 3 discussion; Table S1 |