Lupa-Myszkowska M., Oszajca M., Matoga D. · Chemical Science · 2023 · 14176-14181
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.
Conventional solution and de novo trials did not form Mn-HOF-MA or Mn-HOF-FA, supporting the requirement for mechanochemical grinding.
Caveat: Control experiments were screened by IR/PXRD rather than isolated-product analysis.
p005 · Control experiments · Figures S10-S12
After EIS at elevated temperature and humidity, IR spectra and water sorption remain essentially unchanged, and SEM-EDX indicates retained morphology and homogeneous elemental dispersion.
Caveat: PXRD showed transient new reflections after EIS at high RH, which practically disappeared after a water vapour adsorption-desorption cycle.
p005 · Proton conductive properties · Figures S33-S46 · Linked to 1 structured result
Solvent-free/liquid-assisted mechanochemistry converts non-conductive JUK-1 into proton-conducting Mn-HOF-MA and Mn-HOF-FA by breaking Mn-carboxylate coordination links and forming extended hydrogen-bonded networks.
Caveat: The JUK-1 and JUK-2 precursor recipes are cited from earlier literature and not fully reproduced in this SI.
p003 · Structural details of solid-state reactions · Fig. 2 · Linked to 4 structured results
The solid-state Mn-HOF formations are reversible: Mn-HOF-MA and Mn-HOF-FA return to JUK-1 after immersion in ethanol.
Caveat: Reversibility is evidenced by PXRD after ethanol treatment.
p003 · Postsynthetic modification and physicochemical characterization · Fig. S13
Relative humidity strongly increases proton conductivity, indicating that ions are the primary charge carriers.
Caveat: Mn-HOF-MA and JUK-2 were not measured at 75% RH because of deliquescence.
p004 · Proton conductive properties · Fig. 3, Table S6 · Linked to 5 structured results
Arrhenius activation energies are interpreted as mainly indicating a humidity-independent vehicle mechanism involving diffusion of formamidinium and methylammonium cations.
Caveat: The authors also infer possible pressure/temperature/humidity-induced MHOF phase transitions from two-slope Arrhenius behaviour.
p004 · Proton conductive properties · Fig. S31 · Linked to 3 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| JUK-1 | {[Mn2(ina)4(H2O)2].2EtOH}nDinuclear Mn2 nodes in the parent layered MOF · Isonicotinate (ina) | 2D · PristineLayered non-conductive metal-organic framework used as the precursor for postsynthetic mechanochemical conversion. | p002 · Introduction |
| JUK-2 | {(NH4)2[Mn(ina)2(NCS)2].xH2O}nMn coordination polymer nodes · Isonicotinate, thiocyanate and ammonium cations | 2D · PristineRelated proton-conducting coordination polymer formed from JUK-1 with NH4SCN in prior work and measured here as a comparison material. | p002 · Introduction |
| Mn-HOF-FA | {(CH(NH2)2)2[Mn(ina)2(NCS)2(H2O)2].xH2O}nMononuclear Mn centres with coordinated NCS- and aqua ligands · Isonicotinate, thiocyanate ligands and formamidinium cations in the hydrogen-bonded network | 3D · Pristine3D metal hydrogen-bonded organic framework in which hydrogen bonds interconnect formamidinium cations and [Mn(ina)2(NCS)2(H2O)2]2- complexes. | p004 · Structural details of solid-state reactions |
| Mn-HOF-MA | {(CH3NH3)2[Mn(ina)2(NCS)2(H2O)2].xH2O}nMononuclear Mn centres with coordinated NCS- and aqua ligands · Isonicotinate, thiocyanate ligands and methylammonium cations in the hydrogen-bonded network | 3D · PristineMetal hydrogen-bonded organic framework with intra- and inter-hydrogen-bonded layers; obtained by cleavage of Mn-carboxylate coordination links in JUK-1. | p003 · Postsynthetic modification and physicochemical characterization |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| JUK-1 as-synthesized powderresearch_0771__mat__juk1 | Powder · Pristine Control · Pristine Framework | As-synthesized parent MOF powder | p004 · Synthetic procedures |
| JUK-2 pellet for EISresearch_0771__mat__juk2 | Pellet · Pristine Control · Pristine Framework | Comparison material pellet preconditioned for EIS | p004 · Proton conductive properties |
| Mn-HOF-FA pellet for EISresearch_0771__mat__mn_hof_fa | Pellet · Target Sample · Pristine Framework | Approx. 30 mg preconditioned at RH then pressed between two platinum electrodes | p005-p006 · Samples preparation for EIS measurements; Details of physical measurements |
| Mn-HOF-FA powderresearch_0771__mat__mn_hof_fa | Powder · Target Sample · Pristine Framework | Mechanochemically ground JUK-1 with formamidinium thiocyanate | p004 · Synthesis of Mn-HOF-FA |
| Mn-HOF-MA pellet for EISresearch_0771__mat__mn_hof_ma | Pellet · Target Sample · Pristine Framework | Approx. 30 mg preconditioned at RH then pressed between two platinum electrodes | p005-p006 · Samples preparation for EIS measurements; Details of physical measurements |
| Mn-HOF-MA powderresearch_0771__mat__mn_hof_ma | Powder · Target Sample · Pristine Framework | Mechanochemically ground JUK-1 with methylammonium thiocyanate | p004 · Synthesis of Mn-HOF-MA |