Synthesis · Engineering Band Gap and Photoconduction in Semiconducting Metal Organic Frameworks: Metal Node Effect

6 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

2 · MOF synthesis

Metal precursorsCu(NO3)2.2.5H2O (532 mg, 2.29 mmol)

Linker precursorsTHQ solution (300 mg, 1.74 mmol)

Solventsdegassed H2O (100 mL for metal/en solution; 100 mL for THQ solution)

Additivesethylenediamine (en, 230 mL as reported, 3.45 mmol)

AtmosphereN2 protection

Temperatureroom temperature; drying at 80

Time12 h stirring; 12 h drying

Work-upWashed with H2O (100 mL x 2) and acetone (50 mL x 2).

ActivationDried at 80 oC for 12 h.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	532 mg, 2.29 mmol	2 · MOF synthesis
Linker	THQ	300 mg, 1.74 mmol	2 · MOF synthesis
Base	ethylenediamine (en)	230 mL, 3.45 mmol	2 · MOF synthesis
Solvent	degassed H2O	200 mL total	2 · MOF synthesis
Solvent	acetone	50 mL x 2 wash	2 · MOF synthesis

Complete recipeSource: Both

Route 2: Solvothermal

3 · MOF synthesis

Metal precursorsFeSO4.7H2O (159 mg, 0.57 mmol)

Linker precursorsTHQ (75 mg, 0.44 mmol)

Solventsdegassed H2O (85 mL metal/en solution; 25 mL THQ solution)

Additivesethylenediamine (29 mL as reported, 0.43 mmol)

Atmosphereunder N2; pressure tube

Temperature65; drying at 80

Time12 h heating; 12 h drying

Work-upCooled to room temperature; collected and washed by centrifugation with deionized water (20 mL x 3) and acetone (20 mL x 3).

ActivationDried at 80 oC for 12 h.

Scalability contextReported product mass: 80 mg.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	FeSO4.7H2O	159 mg, 0.57 mmol	3 · MOF synthesis
Linker	THQ	75 mg, 0.44 mmol	3 · MOF synthesis
Base	ethylenediamine	29 mL, 0.43 mmol	3 · MOF synthesis
Solvent	degassed H2O	85 mL + 25 mL	3 · MOF synthesis
Solvent	acetone	20 mL x 3 wash	3 · MOF synthesis

Complete recipeSource: SI

Route 3: Drop Cast

4 · Linear sweeep voltametry (LSV)

SolventsH2O (45 uL), ethanol (135 uL)

AdditivesNafion solution (20 uL binder)

Atmosphereair dried

Time30 min sonication

Substrate orientationFTO slides (1.25 cm x 2.50 cm)

Work-up2 mg MOF suspended in H2O/ethanol/Nafion, sonicated, drop-cast onto clean FTO slides, and air dried.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	MOF sample	2 mg	4 · Linear sweeep voltametry (LSV)
Solvent	H2O	45 uL	4 · Linear sweeep voltametry (LSV)
Solvent	ethanol	135 uL	4 · Linear sweeep voltametry (LSV)
Additive	Nafion solution	20 uL	4 · Linear sweeep voltametry (LSV)
Other	FTO slide	1.25 cm x 2.50 cm	4 · Linear sweeep voltametry (LSV)

Complete recipeSource: SI

Route 4: Other

4 · Figure S3 · Figure S3

Additives3 um mylar spacer; THz-transparent tape

Work-upHole punched through mylar; filled with MOF powder; scraped to remove excess; sandwiched between tape.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	MOF powder	Not specified	4 · Figure S3 · Figure S3
Other	mylar sheet	3 um thick	4 · Figure S3 · Figure S3
Other	THz-transparent tape	two pieces	4 · Figure S3 · Figure S3

Complete recipeSource: Both

Route 5: Solvothermal

3 · MOF synthesis

Metal precursorsNi(OAc)2 (21.21 mg, 0.12 mmol)

Linker precursorsTHQ (10.32 mg, 0.06 mmol)

Solventsdegassed H2O (12 mL); NMP (0.5 mL, 4% cosolvent)

Additivesethylenediamine (6 uL, 0.09 mmol)

AtmosphereN2 purge for 10 min; sealed pressure tube

Temperature85; drying at 80

Time24 h heating; 12 h drying

Work-upCooled to room temperature; collected and washed by centrifugation with deionized water (20 mL x 3) and acetone (20 mL x 3).

ActivationDried at 80 oC for 12 h.

Scalability contextReported yield: 11 mg; tripling the starting materials yielded amorphous solid.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2	21.21 mg, 0.12 mmol	3 · MOF synthesis
Linker	THQ	10.32 mg, 0.06 mmol	3 · MOF synthesis
Solvent	degassed H2O	12 mL	3 · MOF synthesis
Additive	NMP	0.5 mL · 4% cosolvent in water	3 · MOF synthesis
Base	ethylenediamine	6 uL, 0.09 mmol	3 · MOF synthesis

Complete recipeSource: Both

Route 6: Other

2 · MOF synthesis

Metal precursorsZn(NO3)2.2.5H2O (681 mg, 2.29 mmol)

Linker precursorsTHQ solution (300 mg, 1.74 mmol)

Solventsdegassed H2O (100 mL for metal/en solution; 100 mL for THQ solution)

Additivesethylenediamine (en, 115 mL as reported, 3.45 mmol)

AtmosphereN2 protection

Temperatureroom temperature; drying at 80

Time12 h stirring; 12 h drying

Work-upWashed with H2O (100 mL x 2) and acetone (50 mL x 2).

ActivationDried at 80 oC for 12 h.

Scalability contextReported product yield: 90 mg.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.2.5H2O	681 mg, 2.29 mmol	2 · MOF synthesis
Linker	THQ	300 mg, 1.74 mmol	2 · MOF synthesis
Base	ethylenediamine (en)	115 mL, 3.45 mmol	2 · MOF synthesis
Solvent	degassed H2O	200 mL total	2 · MOF synthesis
Solvent	acetone	50 mL x 2 wash	2 · MOF synthesis