Synthesis · Enhancing Electrical Conductivity of Semiconducting MOFs via Defect Healing

7 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Other

2 · Experimental Section

Metal precursorsCo(NO3)2.6H2O, 21 mg (0.072 mmol)

Linker precursorsHAB.3HCl, 10 mg (0.036 mmol)

SolventsH2O, 5 mL for cobalt solution plus 5 mL for linker solution

Additives6 M aqueous NH4OH, 60 uL (0.36 mmol, 10 equiv to HAB)

Atmosphereambient conditions

TemperatureRT

Time1

Work-upDark blue solids centrifuged and washed with H2O and acetone; final products redispersed in H2O for post-treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	21 mg (0.072 mmol)	2 · Experimental Section
Linker	HAB.3HCl	10 mg (0.036 mmol)	2 · Experimental Section
Solvent	H2O	5 mL + 5 mL	2 · Experimental Section
Base	aqueous ammonium hydroxide (NH4OH)	60 uL (0.36 mmol, 10 equiv to HAB) · 6 M	2 · Experimental Section

Partial recipeSource: Both

Route 2: Other

4 · Results and Discussion

Metal precursorsCo3(HAB)2

Linker precursorscorresponding ligand, 0.4 equiv

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Co3(HAB)2	Not specified	4 · Results and Discussion
Linker	corresponding ligand	0.4 equiv	4 · Results and Discussion

Complete recipeSource: Both

Route 3: Other

2 · Experimental Section · HAB-Treatment

Metal precursorsCu3(HAB)2, 5 mg

Linker precursorsHAB.3HCl, 2 mg (7.2 umol)

SolventsH2O, 5 mL for MOF dispersion plus 5 mL for linker solution

Additives6 M aqueous NH4OH, 15 uL

Atmosphereambient atmosphere

TemperatureRT

Time0.5

Work-upResulting dark blue solids centrifuged and washed with H2O and acetone.

ActivationDried under vacuum for 0.5 h at 60 deg C.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3(HAB)2	5 mg	2 · Experimental Section · HAB-Treatment
Linker	HAB.3HCl	2 mg (7.2 umol)	2 · Experimental Section · HAB-Treatment
Solvent	H2O	5 mL + 5 mL	2 · Experimental Section · HAB-Treatment
Base	aqueous ammonium hydroxide (NH4OH)	15 uL · 6 M	2 · Experimental Section · HAB-Treatment

Complete recipeSource: SI

Route 4: Other

S2-S3 · Optimization of HAB-Treatment · Figures S1-S2

Metal precursorspre-synthesised Cu3(HAB)2 MOF

Linker precursorsHAB.3HCl, 0.2 or 0.4 equiv to Cu for ligand-amount screen; 0.4 equiv to Cu for reaction-time screen

SolventsH2O, 5 mL MOF dispersion plus 5 mL linker solution

Additives6 M aqueous NH4OH, 15 uL

Atmosphereambient atmosphere

TemperatureRT; dried at 60 deg C

Time0.25, 0.5, or 1 h depending on time-screen; 0.5 h standard optimum

Work-updark blue solids centrifuged and washed with H2O and acetone

Activationdried under vacuum for 0.5 h at 60 deg C

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3(HAB)2	5 mg	S2-S3 · Optimization of HAB-Treatment · Figures S1-S2
Linker	HAB.3HCl	0.2 equiv or 0.4 equiv to Cu amount	S2-S3 · Optimization of HAB-Treatment · Figures S1-S2
Solvent	H2O	5 mL + 5 mL	S2-S3 · Optimization of HAB-Treatment · Figures S1-S2
Base	aqueous ammonium hydroxide (NH4OH)	15 uL · 6 M	S2-S3 · Optimization of HAB-Treatment · Figures S1-S2

Complete recipeSource: Main

Route 5: Other

2 · Experimental Section

Metal precursorsCu(NO3)2.2.5H2O, 16.8 mg (0.072 mmol)

Linker precursorsHAB.3HCl, 10 mg (0.036 mmol)

SolventsH2O, 10 mL for copper solution plus 5 mL for linker solution

Additives6 M aqueous NH4OH, 60 uL (0.36 mmol, 10 equiv to HAB)

Atmosphereambient conditions

TemperatureRT

Time1

Work-upDark blue solids centrifuged and washed with H2O and acetone; final products redispersed in H2O for post-treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	16.8 mg (0.072 mmol)	2 · Experimental Section
Linker	HAB.3HCl	10 mg (0.036 mmol)	2 · Experimental Section
Solvent	H2O	10 mL + 5 mL	2 · Experimental Section
Base	aqueous ammonium hydroxide (NH4OH)	60 uL (0.36 mmol, 10 equiv to HAB) · 6 M	2 · Experimental Section

Complete recipeSource: Main

Route 6: Other

2 · Experimental Section

Metal precursorsCu(NO3)2.2.5H2O, 16.8 mg (0.072 mmol)

Linker precursorsTATHB.3HCl, 10 mg (0.036 mmol)

SolventsH2O, 5 mL for copper solution plus 5 mL for linker solution

Additives6 M aqueous NH4OH, 60 uL (0.36 mmol, 10 equiv to TATHB)

Atmosphereambient atmosphere

TemperatureRT

Time1

Work-upDark blue solids centrifuged and washed with H2O and acetone; final products redispersed in H2O for post-treatment.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	16.8 mg (0.072 mmol)	2 · Experimental Section
Linker	TATHB.3HCl	10 mg (0.036 mmol)	2 · Experimental Section
Solvent	H2O	5 mL + 5 mL	2 · Experimental Section
Base	aqueous ammonium hydroxide (NH4OH)	60 uL (0.36 mmol, 10 equiv to TATHB) · 6 M	2 · Experimental Section

Partial recipeSource: Both

Route 7: Other

4 · Results and Discussion

Metal precursorsCu3(TATHB)2

Linker precursorscorresponding ligand, 0.4 equiv

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3(TATHB)2	Not specified	4 · Results and Discussion
Linker	corresponding ligand	0.4 equiv	4 · Results and Discussion