Zhang J., Kosaka W., Liu Q. et al. · Journal of the American Chemical Society · 2023 · 26179-26189
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.
O2 can adsorb into/around the framework but does not stabilise the 1e-I state or generate the CO2-induced magnetic/electronic transition.
Caveat: The authors infer only about one equivalent of O2 is in the pores, with additional O2 at surfaces or intercrystal micropores.
p008 · Magnetic properties under O2 · Figure S23 · Linked to 3 structured results
CO2 adsorption changes parent paramagnetic compound 1 into an antiferromagnetic CO2-loaded phase with TN about 62 K, and desorption reverses the transition.
Caveat: Antiferromagnetic phase can be converted to a field-induced ferrimagnet under sufficiently high magnetic field.
p008 · Conclusions · Figure 5 · Linked to 3 structured results
DFT models suggest CO2 does not directly contribute substantially to frontier orbitals, spin density, or exchange; instead, CO2 structurally stabilises the low-valence/electronic state.
Caveat: DFT uses discrete gas-phase models derived from the crystal structure, not periodic electronic transport calculations.
p005 · Structural Characterization of 1-CO2 · Figures S15-S17; Table S4 · Linked to 3 structured results
The CO2-gated sorption and conductivity transitions coincide with a uniform structural phase transition between 1 and 1-CO2, not sample decomposition.
Caveat: Phase boundaries are hysteretic; the authors caution that Clausius-Clapeyron fitting is approximate for this system.
S17 · Structural phase transition induced by CO2 adsorption and CO2 desorption · Figure S11 · Linked to 3 structured results
CO2 adsorption promotes electron hopping by converting TCNQ(OEt)2 from the 2e-I state to the radical-anion 1e-I state, producing reversible conductivity increases under controlled CO2 pressure.
Caveat: Absolute sigma values are mainly graphical, and the reported device uses a two-probe pellet geometry.
p008 · Electrical Conductivity Variation under a CO2 Atmosphere · Figure 6 · Linked to 5 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| DFT model of [{TCNQ(OEt)2 radical}-{Ru(2)2(II,II)}-{TCNQ(OEt)2 radical}]2- | [{TCNQ(OEt)2*-}-{Ru(2)2II,II}-{TCNQ(OEt)2*-}]2- model[Ru(2)2(II,II)] model unit · Two TCNQ(OEt)2 radical-anion moieties with or without nearby CO2 molecules | 0D · Model SystemDiscrete site-A and site-B computational models constructed from SCXRD coordinates for 1-CO2. | p005 · Structural Characterization of 1-CO2 · Figure S14; Table S3 |
| [{Ru2(2,4-F2PhCO2)4}2TCNQ(OEt)2] (1) | [{Ru2(2,4-F2PhCO2)4}2TCNQ(OEt)2]Carboxylate-bridged paddlewheel diruthenium units, including [Ru2(II,III)]+ in the 2e-I assignment · TCNQ(OEt)2 = 2,5-diethoxy-7,7,8,8-tetracyanoquinodimethane; 2,4-difluorobenzoate carboxylates | 2D · PristineParamagnetic 2e-I-type charge-flexible layered donor-acceptor MOF with a two-dimensional fishnet-like network. | p002 · Introduction · Table 1; Scheme 1 |
| CO2-adsorbed [{Ru2(2,4-F2PhCO2)4}2TCNQ(OEt)2] (1-CO2) | C75H36F16N4O24Ru4 for the crystallographic 1-CO2 formula unitCrystallographically independent [Ru(1)2] and [Ru(2)2] units assigned as [Ru(1)2(II,III)]+ and [Ru(2)2(II,II)] in the 1e-I state · TCNQ(OEt)2 radical anion plus 2,4-difluorobenzoate carboxylates; three molar equivalents of CO2 in the pores | 2D · PristineCO2-loaded triclinic P-1 phase preserving the two-dimensional fishnet-like network but with larger void volume and a 1e-I electronic state. | p005 · Structural Characterization of 1-CO2 · Table S1; Figure 2 |
| O2-adsorbed [{Ru2(2,4-F2PhCO2)4}2TCNQ(OEt)2] (1-O2) | [{Ru2(2,4-F2PhCO2)4}2TCNQ(OEt)2] with adsorbed O2Diruthenium paddlewheel units retained in the parent framework · TCNQ(OEt)2 and 2,4-difluorobenzoate ligands | 2D · PristineO2-loaded control phase that remains paramagnetic and in the 2e-I state. | S37 · Magnetic property under O2 atmosphere · Figure S23 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| Activated crystals of compound 1research_0761__mat__ru_tcnq_mof_1 | Single Crystal · Target Sample · Pristine Framework | Block-shaped dark brown 1-PhH crystals heated at 400 K under vacuum for 12 h to remove benzene and form 1. | p009 · Materials and Synthesis |
| DFT site-A model with and without CO2research_0761__mat__ru_tcnq_dft_model | Model · Model System · Model | Discrete model constructed from 1-CO2 SCXRD coordinates; compared with and without two CO2 molecules. | S22 · Calculated results · Figure S14 |
| DFT site-B model with and without CO2research_0761__mat__ru_tcnq_dft_model | Model · Model System · Model | Discrete site-B model constructed from 1-CO2 SCXRD coordinates; compared with and without two CO2 molecules. | S22 · Calculated results · Figure S14 |
| O2-loaded compound 1 magnetic controlresearch_0761__mat__ru_tcnq_mof_1_o2 | Powder · Pristine Control · Guest Loaded | Sample of 1 exposed to 100 kPa O2 at 200 K, cooled to 90 K and equilibrated for 6 h before magnetic measurements.SQUID cell | S37 · Magnetic property under O2 atmosphere · Figure S23 |
| CO2-dosed pellet of compound 1 during conductivity switchingresearch_0761__mat__ru_tcnq_mof_1_co2 | Pellet · Target Sample · Guest Loaded | Same pelletized sample of 1 under controlled CO2 pressure, switching between vacuum 1 and CO2-loaded 1-CO2.stainless-steel plate electrodes with Au wires/Au paste · pellet diameter 10 mm; thickness approximately 0.1 mm | p007 · Electrical Conductivity Variation under a CO2 Atmosphere · Figure 6 |
| Pelletized compound 1 for DC conductivityresearch_0761__mat__ru_tcnq_mof_1 | Pellet · Target Sample · Pristine Framework | Microcrystalline powder compressed into a pellet and dried under high vacuum before gas-controlled conductivity measurements.stainless-steel plate electrodes with Au wires/Au paste · pellet diameter 10 mm; thickness approximately 0.1 mm | p009 · In Situ DC Conductivity Measurements under CO2 |
| CO2-dosed single crystal of 1 for SCXRDresearch_0761__mat__ru_tcnq_mof_1_co2 | Single Crystal · Target Sample · Guest Loaded | Single crystal of 1 dosed with 100 kPa CO2 at room temperature and slowly cooled to 195 K.silica glass capillary wall with epoxy adhesive · crystal dimensions 0.112 x 0.045 x 0.045 mm3 | p009 · Single Crystal X-ray Crystallography · Table S1 |