Synthesis · Porous, conductive metal-triazolates and their structural elucidation by the charge-flipping method

7 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Solvothermal

SI p.3 · Synthesis of MET-1 · Section S1

Metal precursorsMgCl2 (4 mmol)

Linker precursors1H-1,2,3-triazole (10 mmol)

SolventsN,N-diethylformamide (DEF), 12 mL

Atmosphereambient laboratory conditions; no precautions to exclude oxygen/moisture

Temperature120

Time240

Work-upDEF wash three times; methanol immersion 3 days with three exchanges; decant

Activationvacuum (10^-5 Torr) 24 h at 100 C; stored in desiccator

Scalability contextMicrocrystalline powder product; no scale-up study reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	MgCl2	4 mmol	SI p.3 · Synthesis of MET-1 · Section S1
Linker	1H-1,2,3-triazole	10 mmol	SI p.3 · Synthesis of MET-1 · Section S1
Solvent	N,N-diethylformamide (DEF), 12 mL	Not specified	SI p.3 · Synthesis of MET-1 · Section S1

Complete recipeSource: Both

Route 2: Solvothermal

SI p.3 · Synthesis of MET-2 · Section S1

Metal precursorsMn(NO3)2.4H2O (1 mmol)

Linker precursors1H-1,2,3-triazole (2.5 mmol)

SolventsN,N-diethylformamide (DEF), 10 mL

Atmosphereambient laboratory conditions; no precautions to exclude oxygen/moisture

Temperature120

Time24

Work-upDEF wash three times; methanol immersion 3 days with three exchanges; decant

Activationvacuum (10^-5 Torr) 24 h at room temperature; stored in desiccator

Scalability contextMicrocrystalline powder product; no scale-up study reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Mn(NO3)2.4H2O	1 mmol	SI p.3 · Synthesis of MET-2 · Section S1
Linker	1H-1,2,3-triazole	2.5 mmol	SI p.3 · Synthesis of MET-2 · Section S1
Solvent	N,N-diethylformamide (DEF), 10 mL	Not specified	SI p.3 · Synthesis of MET-2 · Section S1

Partial recipeSource: Main

Route 3: Other

p.5, article p.10599 · Electrical conductivity · Figure 6b

Metal precursorsMET-3 pressed pellet

Linker precursorspreformed MET-3 framework

AdditivesI2 vapour

Atmosphereiodine vapour exposure; exact vapour pressure not reported

Temperaturenot reported

Time0.667

Oxidant / reductantI2 as oxidising dopant; authors propose FeII oxidation to FeIII

Work-upPXRD checked after pellet formation and I2 exposure

Activationnot applicable beyond iodine exposure

Scalability contextDoping reported only as a pellet exposure experiment.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	MET-3 pressed pellet	Not specified	p.5, article p.10599 · Electrical conductivity · Figure 6b
Oxidant	I2 vapour	40 min exposure	p.5, article p.10599 · Electrical conductivity · Figure 6b

Complete recipeSource: SI

Route 4: Solvothermal

SI p.4 · Synthesis of MET-3 · Section S1

Metal precursorsFeCl2 (0.5 mmol)

Linker precursors1H-1,2,3-triazole (1.5 mmol)

Solventsanhydrous N,N-dimethylformamide (DMF), 3 mL

Atmosphereanhydrous Ar; Schlenk line; evacuated/refilled with Ar three times; sealed under <=150 mTorr after liquid-N2 freeze

Temperature120

Time48

Work-upcentrifuged; washed with 15 mL DMF three times; methanol immersion 3 days with three exchanges; decant

Activationvacuum (10^-5 Torr) 24 h at 100 C; stored in desiccator

Scalability contextMicrocrystalline powder product; no scale-up study reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	FeCl2	0.5 mmol	SI p.4 · Synthesis of MET-3 · Section S1
Linker	1H-1,2,3-triazole	1.5 mmol	SI p.4 · Synthesis of MET-3 · Section S1
Solvent	anhydrous N,N-dimethylformamide (DMF), 3 mL	Not specified	SI p.4 · Synthesis of MET-3 · Section S1

Complete recipeSource: SI

Route 5: Solvothermal

SI pp.4-5 · Synthesis of MET-4 · Section S1

Metal precursorsCoCl2 (0.5 mmol)

Linker precursors1H-1,2,3-triazole (1.5 mmol)

Solventsanhydrous N,N-dimethylformamide (DMF), 3 mL

Atmosphereanhydrous Ar; Schlenk line; evacuated/refilled with Ar three times; sealed under <=150 mTorr after liquid-N2 freeze

Temperature120

Time48

Work-upwashed with 15 mL DMF three times; methanol immersion 3 days with three exchanges; decant

Activationvacuum (10^-5 Torr) 24 h at 100 C; stored in desiccator

Scalability contextMicrocrystalline powder product; no scale-up study reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CoCl2	0.5 mmol	SI pp.4-5 · Synthesis of MET-4 · Section S1
Linker	1H-1,2,3-triazole	1.5 mmol	SI pp.4-5 · Synthesis of MET-4 · Section S1
Solvent	anhydrous N,N-dimethylformamide (DMF), 3 mL	Not specified	SI pp.4-5 · Synthesis of MET-4 · Section S1

Complete recipeSource: SI

Route 6: Solvothermal

SI p.5 · Synthesis of MET-5 · Section S1

Metal precursorsCu(NO3)2.xH2O (1 mmol)

Linker precursors1H-1,2,3-triazole (3 mmol)

SolventsN,N-diethylformamide (DEF), 10 mL

Atmosphereambient laboratory conditions; capped vial

Temperature100

Time26

Work-uproom temperature 8 h before heating; filtrated; washed with DEF three times; methanol immersion 3 days with three exchanges; decant

Activationvacuum (10^-5 Torr) 24 h at room temperature; stored in desiccator

Scalability contextMicrocrystalline powder product; no scale-up study reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.xH2O	1 mmol	SI p.5 · Synthesis of MET-5 · Section S1
Linker	1H-1,2,3-triazole	3 mmol	SI p.5 · Synthesis of MET-5 · Section S1
Solvent	N,N-diethylformamide (DEF), 10 mL	Not specified	SI p.5 · Synthesis of MET-5 · Section S1

Complete recipeSource: SI

Route 7: Other

SI p.5 · Synthesis of MET-6 · Section S1

Metal precursorsZnCl2 (1.00 g (7.34 mmol))

Linker precursors1H-1,2,3-triazole (1.25 mL (21.6 mmol), dropwise)

SolventsDMF 10 mL; ethanol 10 mL; water 15 mL

Additivesammonium hydroxide (30%), 5 mL

Atmosphereambient laboratory conditions; stirred suspension

Temperatureroom temperature

Time24

Work-upwhite precipitate filtered; rinsed with DMF and methanol; methanol immersion 3 days with three exchanges; decant

Activationvacuum (10^-5 Torr) 24 h at room temperature; stored in desiccator

Scalability contextMicrocrystalline powder product; no scale-up study reported.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZnCl2	1.00 g (7.34 mmol)	SI p.5 · Synthesis of MET-6 · Section S1
Linker	1H-1,2,3-triazole	1.25 mL (21.6 mmol), dropwise	SI p.5 · Synthesis of MET-6 · Section S1
Solvent	DMF 10 mL	Not specified	SI p.5 · Synthesis of MET-6 · Section S1
Solvent	ethanol 10 mL	Not specified	SI p.5 · Synthesis of MET-6 · Section S1
Solvent	water 15 mL	Not specified	SI p.5 · Synthesis of MET-6 · Section S1
Base	ammonium hydroxide (30%), 5 mL	Not specified	SI p.5 · Synthesis of MET-6 · Section S1