Synthesis · Super Proton Conductivity Through Control of Hydrogen-Bonding Networks in Flexible Metal–Organic Frameworks

10 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Other

S3 · Vapor Diffusion Method · Figure S26

Metal precursorsMIL-101 powder

Solventsimidazole vapour from neat imidazole

Additivesimidazole

AtmosphereTeflon-lined autoclave; atmosphere not specified

Temperature150

Time48

Work-upnot specified

Activationsame parent activation method as Im@MIL-88B-LB implied

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	MIL-101 powder	not stated	S3 · Vapor Diffusion Method · Figure S26
Other	imidazole	not separately stated; same method as Im@MIL-88B-LB	S3 · Vapor Diffusion Method · Figure S26

Complete recipeSource: SI

Route 2: Other

S3-S4 · Solution-based Method · Table S2

Metal precursorsactivated MIL-88B powder (50 mg)

SolventsMeOH

Additivesimidazole solution

Atmosphereroom-temperature solution immersion; atmosphere not specified

Temperatureroom temperature

Time48

Work-upfilter crystals

Activationdry at 40 deg C for 12 h under vacuum

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	activated MIL-88B powder	50 mg	S3-S4 · Solution-based Method · Table S2
Other	imidazole in MeOH	not stated · 1 M	S3-S4 · Solution-based Method · Table S2
Solvent	MeOH	not stated	S3-S4 · Solution-based Method · Table S2

Complete recipeSource: Both

Route 3: Other

S3 · Vapor Diffusion Method · Table S2; Figure S9

Metal precursorsactivated MIL-88B powder (50 mg)

Solventsimidazole vapour from neat imidazole

Additivesimidazole (1.36 g)

AtmosphereTeflon-lined autoclave; under vacuum activation before loading; atmosphere during loading not specified

Temperature150

Time48

Work-upnot specified after loading

Activationparent powder activated at 120 deg C under vacuum for 12 h before loading

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	activated MIL-88B powder	50 mg	S3 · Vapor Diffusion Method · Table S2; Figure S9
Other	imidazole	1.36 g	S3 · Vapor Diffusion Method · Table S2; Figure S9

Complete recipeSource: Both

Route 4: Other

S3 · Solution-based Method · Table S4

Metal precursorsactivated MIL-88B-NH2 (50 mg)

SolventsMeOH

Additives1 M imidazole solution

Atmosphereroom-temperature solution immersion; atmosphere not specified

Temperatureroom temperature

Time48

Work-upfilter crystals

Activationdry at 40 deg C for 12 h under vacuum

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	activated MIL-88B-NH2	50 mg	S3 · Solution-based Method · Table S4
Other	imidazole solution in MeOH	not stated · 1 M	S3 · Solution-based Method · Table S4
Solvent	MeOH	not stated	S3 · Solution-based Method · Table S4

Complete recipeSource: Both

Route 5: Other

S3 · Vapor Diffusion Method · Figure 2; Table S4

Metal precursorsactivated MIL-88B powder (50 mg)

Solventsimidazole vapour from neat imidazole

Additivesimidazole (1.36 g)

AtmosphereTeflon-lined autoclave; under vacuum activation before loading; atmosphere during loading not specified

Temperature120

Time48

Work-upnot specified after loading

Activationparent powder activated at 120 deg C under vacuum for 12 h before loading

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	activated MIL-88B powder	50 mg	S3 · Vapor Diffusion Method · Figure 2; Table S4
Other	imidazole	1.36 g	S3 · Vapor Diffusion Method · Figure 2; Table S4

Complete recipeSource: Both

Route 6: Other

S3 · Solution-based Method · Table S4

Metal precursorsactivated MIL-88B-SO3H (50 mg)

SolventsMeOH

Additives1 M imidazole solution

Atmosphereroom-temperature solution immersion; atmosphere not specified

Temperatureroom temperature

Time48

Work-upfilter crystals

Activationdry at 40 deg C for 12 h under vacuum

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	activated MIL-88B-SO3H	50 mg	S3 · Solution-based Method · Table S4
Other	imidazole solution in MeOH	not stated · 1 M	S3 · Solution-based Method · Table S4
Solvent	MeOH	not stated	S3 · Solution-based Method · Table S4

Complete recipeSource: SI

Route 7: Solvothermal

S3 · Synthesis of MIL-101

Metal precursorsFeCl3.6H2O (2.45 mmol, 675 mg)

Linker precursorsH2BDC (1.24 mmol, 206 mg)

SolventsDMF (15 mL)

Additivessonication

AtmosphereTeflon-lined autoclave; atmosphere not specified

Temperature110

Time20

Work-upcool to room temperature; centrifuge; wash three times with DMF and EtOH

Activationdry at 80 deg C overnight under vacuum

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	FeCl3.6H2O	2.45 mmol, 675 mg	S3 · Synthesis of MIL-101
Linker	H2BDC	1.24 mmol, 206 mg	S3 · Synthesis of MIL-101
Solvent	DMF	15 mL	S3 · Synthesis of MIL-101

Complete recipeSource: SI

Route 8: Hydrothermal

S2 · Synthesis of MIL-88B-NH2

Metal precursorsFeCl3.6H2O (1.33 mmol, 360 mg)

Linker precursors2-aminoterephthalic acid; amount not stated in text layer

SolventsDI water (30 mL)

Additivespluronic F-127 (320 mg); acetic acid (0.6 mL)

AtmosphereTeflon-lined autoclave; atmosphere not specified

Temperature110

Time24

Work-upcool to room temperature; centrifuge; wash 3 times with EtOH and DMF

Activationdry at 80 deg C overnight under vacuum

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	FeCl3.6H2O	1.33 mmol, 360 mg	S2 · Synthesis of MIL-88B-NH2
Linker	2-aminoterephthalic acid	not stated in text layer	S2 · Synthesis of MIL-88B-NH2
Solvent	DI water	30 mL	S2 · Synthesis of MIL-88B-NH2
Additive	pluronic F-127	320 mg	S2 · Synthesis of MIL-88B-NH2
Acid	acetic acid	0.6 mL	S2 · Synthesis of MIL-88B-NH2

Complete recipeSource: SI

Route 9: Solvothermal

S2-S3 · Synthesis of MIL-88B-SO3H · Table S1

Metal precursorsFe(NO3)3.9H2O (1 mmol, 404 mg)

Linker precursorsH2BDC-SO3Na (1 mmol, 268 mg)

SolventsEtOH (5 mL) and DI water (5 mL)

Atmospherepressure tube; atmosphere not specified

Temperature100

Time6

Work-upcool to room temperature; centrifuge; wash 3 times with EtOH and DMF; soak in DI water to remove sodium ions; wash with EtOH 3 times

Activationdry at 60 deg C overnight under vacuum, then dry final powder at 60 deg C under vacuum

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Fe(NO3)3.9H2O	1 mmol, 404 mg	S2-S3 · Synthesis of MIL-88B-SO3H · Table S1
Linker	H2BDC-SO3Na	1 mmol, 268 mg	S2-S3 · Synthesis of MIL-88B-SO3H · Table S1
Solvent	EtOH	5 mL	S2-S3 · Synthesis of MIL-88B-SO3H · Table S1
Solvent	DI water	5 mL	S2-S3 · Synthesis of MIL-88B-SO3H · Table S1

Complete recipeSource: SI

Route 10: Solvothermal

S2 · Synthesis of MIL-88B

Metal precursorsFe(NO3)3.9H2O (0.8 mmol, 323.2 mg)

Linker precursorsH2BDC (0.8 mmol, 132.8 mg)

SolventsACN (5 mL) and DMF (5 mL)

Atmospherepressure tube; atmosphere not specified

Temperature100

Time6

Work-upcool to room temperature; centrifuge; wash 3 times with EtOH and DMF

Activationdry at 80 deg C overnight under vacuum

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Fe(NO3)3.9H2O	0.8 mmol, 323.2 mg	S2 · Synthesis of MIL-88B
Linker	H2BDC	0.8 mmol, 132.8 mg	S2 · Synthesis of MIL-88B
Solvent	ACN	5 mL	S2 · Synthesis of MIL-88B
Solvent	DMF	5 mL	S2 · Synthesis of MIL-88B