cMOF Evidence Base

Synthesis evidence

Mixed proton-electron conductivity in a dynamic 3D metal-organic framework

Rambabu D., Goossens T., Bakuru V.R. et al. · Chem · 2025 · 102590

15 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Complete recipeSource: Both

Route 1: Other

p010 · Dehydration of H12-M2-(DOBDP)3_h MOFs

Atmospherevacuum inside an Ar-filled glovebox
Temperature150
Time5
Work-upfully dehydrated sample used for conductivity and redox processing
Activationheating in Buchi glass oven under vacuum at 150 deg C for 5 h
Complete recipeSource: Both

Route 2: Hydrothermal

p010 · Synthetic procedures · Figure S2

Metal precursorsAl(NO3)3.9H2O
Linker precursorsH6-DOBDP
Solventsdeionised water
Atmosphereambient/air; capped vial
Temperature40
Time336
Work-upoff-white crystalline powder separated by filtration, washed with deionised water (5 mL, 3 times), dried in open ambient air
Activationopen-air drying; no additional activation before pristine use
Scalability context40 deg C powder yield 72 mg, 67% based on H12-Al2-(DOBDP)3.12H2O; RT route also gave same product after 1 month with 31 mg, 29% yield.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
LinkerH6-DOBDP0.3 mmolp010 · Synthetic procedures · Figure S2
Metal SourceAl(NO3)3.9H2O0.2 mmolp010 · Synthetic procedures · Figure S2
Solventdeionized water3 mLp010 · Synthetic procedures · Figure S2
Complete recipeSource: Both

Route 3: Other

p010 · Dehydration of H12-M2-(DOBDP)3_h MOFs

Atmospherevacuum at room temperature
Temperatureroom temperature
Time10
Work-uppartially hydrated Al sample analysed by XRD/transport
Activationvacuum at RT for 10 h
Complete recipeSource: Both

Route 4: Other

p010 · Synthetic procedures

Metal precursorsAl(NO3)3.9H2O
Linker precursorsH6-DOBDP
Solventsdeionised water
Atmosphereambient/air; capped vial
Temperatureroom temperature
Timeapproximately 17520
Work-upsuitable crystals used for single-crystal XRD
Activationnone reported for single crystals
Scalability contextVery long crystallisation time: 2 years.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
LinkerH6-DOBDP0.3 mmolp010 · Synthetic procedures
Metal SourceAl(NO3)3.9H2O0.2 mmolp010 · Synthetic procedures
Solventdeionized water3 mLp010 · Synthetic procedures
Complete recipeSource: Both

Route 5: Other

p011 · Chemical oxidation-reduction of H12-M2-(DOBDP)3 (M = Fe, Al) · Figure 5; Figure S25

Solventsacetonitrile for oxidation; methanol for reduction
AtmosphereAr-filled glovebox
Temperatureroom temperature for oxidation; 150 deg C drying after reduction
Time36 for oxidation
Oxidant / reductantNOBF4 oxidant; NaBH3CN reductant
Work-upoxidised suspensions centrifuged, washed with acetonitrile (3 x 5 mL), dried under vacuum at RT; reduced samples dried at 150 deg C under vacuum
Activationchemical oxidation/reduction of dehydrated H12-M2-(DOBDP)3_d (M = Al, Fe)
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
OxidantNOBF40.26 mmol, 6.5 equivp011 · Chemical oxidation-reduction of H12-M2-(DOBDP)3 (M = Fe, Al) · Figure 5; Figure S25
Reductantsodium cyanoborohydride (NaBH3CN)6.5 equivp011 · Chemical oxidation-reduction of H12-M2-(DOBDP)3 (M = Fe, Al) · Figure 5; Figure S25
Solventacetonitrile5 mL MOF suspension + 5 mL oxidant solutionp011 · Chemical oxidation-reduction of H12-M2-(DOBDP)3 (M = Fe, Al) · Figure 5; Figure S25
Solventmethanolused for reductionp011 · Chemical oxidation-reduction of H12-M2-(DOBDP)3 (M = Fe, Al) · Figure 5; Figure S25
Complete recipeSource: Both

Route 6: Other

p010 · Dehydration of H12-M2-(DOBDP)3_h MOFs

Atmospherevacuum inside an Ar-filled glovebox
Temperature150
Time5
Work-upfully dehydrated sample used for XRD, conductivity and redox processing
Activationheating in Buchi glass oven under vacuum at 150 deg C for 5 h
Complete recipeSource: Both

Route 7: Hydrothermal

p010 · Synthetic procedures · Figure S1

Metal precursorsFe(NO3)3.9H2O
Linker precursorsH6-DOBDP
Solventsdeionised water
Additivesconcentrated HCl
Atmosphereambient/air; capped vial
Temperature40
Time72
Work-updark yellow solid separated by filtration, washed with deionised water (5 mL, 3 times), dried in open ambient air
Activationopen-air drying; no additional activation before pristine use
Scalability contextYield 81 mg, 72% based on H12-Fe2-(DOBDP)3.12H2O; powder XRD confirmed phase purity.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerH6-DOBDP0.3 mmolp010 · Synthetic procedures · Figure S1
Metal SourceFe(NO3)3.9H2O0.2 mmolp010 · Synthetic procedures · Figure S1
Acidconcentrated HCl200 uL · 37% reagent listedp010 · Synthetic procedures · Figure S1
Solventdeionized water2 mL for linker; 1 mL for Fe saltp010 · Synthetic procedures · Figure S1
Partial recipeSource: Both

Route 8: Other

p010 · Dehydration of H12-M2-(DOBDP)3_h MOFs

Atmospherevacuum under inert conditions
Work-upmetastable partial dehydrated sample handled under inert conditions
Activationvacuum under inert conditions
Complete recipeSource: Both

Route 9: Other

p010 · Dehydration of H12-M2-(DOBDP)3_h MOFs

Atmospherevacuum at room temperature
Temperatureroom temperature
Time10
Work-uppartially hydrated sample analysed by XRD/transport
Activationvacuum at RT for 10 h
Complete recipeSource: Both

Route 10: Hydrothermal

p010 · Synthetic procedures · Figure S1

Metal precursorsFe(ClO4)2.xH2O
Linker precursorsH6-DOBDP
Solventsdeionised water
Atmosphereambient/air; capped vial
Temperature70
Time48
Work-upyellow product comprising single hexagonal crystals and powder was filtered, washed with deionised water (5 mL x 3), left to dry in ambient air; single crystals manually separated
Activationnone beyond ambient drying
Scalability contextBulk powder from this single-crystal route was phase impure; a separate pure-powder route was developed.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
LinkerH6-DOBDP0.2 mmolp010 · Synthetic procedures · Figure S1
Metal SourceFe(ClO4)2.xH2O0.2 mmol, calculated on an anhydrous basisp010 · Synthetic procedures · Figure S1
Solventdeionized water2 mL for linker; 1 mL for Fe saltp010 · Synthetic procedures · Figure S1
Complete recipeSource: Both

Route 11: Hydrothermal

p010 · Synthetic procedures

Metal precursorsIn(NO3)2.xH2O
Linker precursorsH6-DOBDP
Solventsdeionised water
Atmosphereambient/air; capped vial
Temperature40
Time120
Work-upwhite solid filtered, washed with deionised water (5 mL, 3 times), dried in open ambient air
Activationopen-air drying; no additional activation before pristine use
Scalability contextYield 76 mg, 56% based on H12-In2-(DOBDP)3.18H2O.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
LinkerH6-DOBDP0.3 mmolp010 · Synthetic procedures
Metal SourceIn(NO3)2.xH2O0.2 mmol, calculated on anhydrous basisp010 · Synthetic procedures
Solventdeionized water2 mL for linker; 1 mL for In saltp010 · Synthetic procedures
Complete recipeSource: Both

Route 12: Other

p010 · Rehydration of _ph, _pd, and _d MOFs · Figure S9

Solventswater
Atmosphereambient or heated aqueous exposure depending on metal and starting hydration state
Temperatureroom temperature or 70
Time1 or 168 depending on phase/metal
Work-upexcess water removed by filtration; rehydrated phases analysed by XRD
Activationwater exposure
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
Solventwaterexcess; removed by filtrationp010 · Rehydration of _ph, _pd, and _d MOFs · Figure S9
Complete recipeSource: Both

Route 13: Hydrothermal

p010 · Synthetic procedures

Metal precursorsSc(CF3SO3)3
Linker precursorsH6-DOBDP
Solventsdeionised water
Atmosphereambient/air; capped vial
Temperature40
Time120
Work-upwhite solid filtered, washed with deionised water (5 mL, 3 times), dried in open ambient air
Activationopen-air drying; no additional activation before pristine use
Scalability contextYield 87 mg, 67% based on H12-Sc2-(DOBDP)3.18H2O.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
LinkerH6-DOBDP0.3 mmolp010 · Synthetic procedures
Metal SourceSc(CF3SO3)30.2 mmolp010 · Synthetic procedures
Solventdeionized water2 mL for linker; 1 mL for Sc saltp010 · Synthetic procedures
Complete recipeSource: Both

Route 14: Other

p010 · Dehydration of H12-M2-(DOBDP)3_h MOFs

Atmospherevacuum inside an Ar-filled glovebox
Temperature150
Time5
Work-upfully dehydrated Sc/In phases analysed by XRD/FTIR/CHN
Activationheating in Buchi glass oven under vacuum at 150 deg C for 5 h
Partial recipeSource: Both

Route 15: Hydrothermal

p010 · Synthetic procedures · Figure 1; Figure S5

Metal precursorsquaternary mixture of Fe, Al, Sc and In metal precursors
Linker precursorsH6-DOBDP
Solventsdeionised water
Additivesconcentrated HCl, by adoption of Fe bulk protocol
Atmosphereambient/air; capped vial
Temperature40
Time72
Work-upsame protocol as H12-Fe2-(DOBDP)3_h bulk crystalline powder; workup therefore filtration, water washing and open-air drying
Activationopen-air drying; no additional activation reported
Scalability contextUsed 0.025 mmol of each metal precursor; final Fe:Al:Sc:In = 0.31:0.06:0.44:0.19 by ICP-OES.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourceeach metal precursor0.025 mmol eachp010 · Synthetic procedures · Figure 1; Figure S5
LinkerH6-DOBDPas in Fe bulk protocol, 0.3 mmolp010 · Synthetic procedures · Figure 1; Figure S5
Acidconcentrated HClas in Fe bulk protocol, 200 uL · 37% reagent listedp010 · Synthetic procedures · Figure 1; Figure S5
Solventdeionized wateras in Fe bulk protocolp010 · Synthetic procedures · Figure 1; Figure S5