Synthesis · Highly conductive three-dimensional metal organic frameworks from small in situ generated ligands

8 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Solvothermal

p006-p007 · Synthetic procedures · Method B

Metal precursorscobalt chloride, 2 mmol

Linker precursorsNo pre-synthesised linker; formate generated in situ from DMF

Solvents8 mL deionised water and 8 mL DMF

AdditivesNone reported

AtmosphereAutogenous pressure in sealed Teflon-lined stainless-steel autoclave

Temperature120; 90

Time72; 48

Work-upSlowly cooled to room temperature at 10 C h^-1, reheated at 90 C for 2 days, then cooled to room temperature to obtain crystals

ActivationNone for as-synthesised crystals

Scalability contextAuthors state the strategy is reproducible and can produce highly crystalline MOFs in bulk.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	cobalt chloride	2 mmol	p006-p007 · Synthetic procedures · Method B
Solvent	deionised water	8 mL	p006-p007 · Synthetic procedures · Method B
Solvent	DMF (N,N-dimethylformamide)	8 mL	p006-p007 · Synthetic procedures · Method B

Partial recipeSource: Main

Route 2: Other

p005 · Results and discussion · Table 4

Metal precursorsAs-synthesised MOF framework

Linker precursorsFormate framework retained after guest removal, according to PXRD discussion

Atmospherenot reported

Temperature160

Time24

Oxidant / reductantThermal removal/neutralisation of dimethylammonium guest; possible hydronium generation and Co/Ni oxidation discussed

Work-upHeated MOF at 160 C for 24 h; pellet preparation details otherwise follow conductivity measurement section

ActivationHeating at 160 C for 24 h to remove guests

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	as-synthesised Co-F	not reported	p005 · Results and discussion · Table 4

Partial recipeSource: Main

Route 3: Other

p005 · Results and discussion · Table 4

Metal precursorsAs-synthesised MOF framework

Linker precursorsFormate framework retained after guest removal, according to PXRD discussion

Atmospherenot reported

Temperature160

Time24

Oxidant / reductantThermal removal/neutralisation of dimethylammonium guest; possible hydronium generation and Co/Ni oxidation discussed

Work-upHeated MOF at 160 C for 24 h; pellet preparation details otherwise follow conductivity measurement section

ActivationHeating at 160 C for 24 h to remove guests

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	as-synthesised Mn-F	not reported	p005 · Results and discussion · Table 4

Partial recipeSource: Main

Route 4: Other

p005 · Results and discussion · Table 4

Metal precursorsAs-synthesised MOF framework

Linker precursorsFormate framework retained after guest removal, according to PXRD discussion

Atmospherenot reported

Temperature160

Time24

Oxidant / reductantThermal removal/neutralisation of dimethylammonium guest; possible hydronium generation and Co/Ni oxidation discussed

Work-upHeated MOF at 160 C for 24 h; pellet preparation details otherwise follow conductivity measurement section

ActivationHeating at 160 C for 24 h to remove guests

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	as-synthesised Ni-F	not reported	p005 · Results and discussion · Table 4

Partial recipeSource: Main

Route 5: Other

p005 · Results and discussion · Table 4

Metal precursorsAs-synthesised MOF framework

Linker precursorsFormate framework retained after guest removal, according to PXRD discussion

Atmospherenot reported

Temperature160

Time24

Oxidant / reductantThermal removal/neutralisation of dimethylammonium guest; possible hydronium generation and Co/Ni oxidation discussed

Work-upHeated MOF at 160 C for 24 h; pellet preparation details otherwise follow conductivity measurement section

ActivationHeating at 160 C for 24 h to remove guests

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	as-synthesised Zn-F	not reported	p005 · Results and discussion · Table 4

Complete recipeSource: Main

Route 6: Solvothermal

p006 · Synthetic procedures · Method A

Metal precursorsManganese chloride, 2 mmol

Linker precursorsNo pre-synthesised linker; formate generated in situ from DMF

Solvents15 mL DMF

Additives2 mL dilute hydrochloric acid

AtmosphereAutogenous pressure in sealed Teflon-lined stainless-steel autoclave

Temperature120

Time48

Work-upCooled to room temperature at 10 C h^-1; crystals collected and dried at room temperature overnight

ActivationNone for as-synthesised crystals

Scalability contextAuthors state the strategy is reproducible and can produce highly crystalline MOFs in bulk.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	manganese chloride	2 mmol	p006 · Synthetic procedures · Method A
Solvent	DMF (N,N-dimethylformamide)	15 mL	p006 · Synthetic procedures · Method A
Acid	dilute hydrochloric acid	2 mL	p006 · Synthetic procedures · Method A

Complete recipeSource: Main

Route 7: Solvothermal

p006-p007 · Synthetic procedures · Method B

Metal precursorsnickel chloride, 2 mmol

Linker precursorsNo pre-synthesised linker; formate generated in situ from DMF

Solvents8 mL deionised water and 8 mL DMF

AdditivesNone reported

AtmosphereAutogenous pressure in sealed Teflon-lined stainless-steel autoclave

Temperature120; 90

Time72; 48

Work-upSlowly cooled to room temperature at 10 C h^-1, reheated at 90 C for 2 days, then cooled to room temperature to obtain crystals

ActivationNone for as-synthesised crystals

Scalability contextAuthors state the strategy is reproducible and can produce highly crystalline MOFs in bulk.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel chloride	2 mmol	p006-p007 · Synthetic procedures · Method B
Solvent	deionised water	8 mL	p006-p007 · Synthetic procedures · Method B
Solvent	DMF (N,N-dimethylformamide)	8 mL	p006-p007 · Synthetic procedures · Method B

Complete recipeSource: Main

Route 8: Solvothermal

p006-p007 · Synthetic procedures · Method B

Metal precursorszinc chloride, 2 mmol

Linker precursorsNo pre-synthesised linker; formate generated in situ from DMF

Solvents8 mL deionised water and 8 mL DMF

AdditivesNone reported

AtmosphereAutogenous pressure in sealed Teflon-lined stainless-steel autoclave

Temperature120; 90

Time72; 48

Work-upSlowly cooled to room temperature at 10 C h^-1, reheated at 90 C for 2 days, then cooled to room temperature to obtain crystals

ActivationNone for as-synthesised crystals

Scalability contextAuthors state the strategy is reproducible and can produce highly crystalline MOFs in bulk.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	zinc chloride	2 mmol	p006-p007 · Synthetic procedures · Method B
Solvent	deionised water	8 mL	p006-p007 · Synthetic procedures · Method B
Solvent	DMF (N,N-dimethylformamide)	8 mL	p006-p007 · Synthetic procedures · Method B