Synthesis · Solvent-Directed Assembly of π-Stacked 3D Metal-Organic Frameworks with Tunable Conductivity Enhanced by C60 Encapsulation

8 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Solvothermal

SI p004 / S4 · Synthesis of NU-4000

Metal precursorsCuCl2 (3.00 mg, 22.3 x 10-3 mmol)

Linker precursorsH6L (2.00 mg, 2.10 x 10-3 mmol)

SolventsDMF (200 uL), toluene (250 uL), H2O (50 uL)

Atmospheresealed 1.5-dram vial; atmosphere not otherwise specified

Temperature100

Time12

Work-upAfter cooling, crystals collected by centrifugation; washed with DMF (5 mL x 3) and acetone (5 mL x 3); soaked in acetone overnight; washed with acetone three more times.

Activation80 C overnight under dynamic vacuum

Scalability contextmilligram-scale vial synthesis; no scale-up demonstrated

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H6L	2.00 mg; 2.10 x 10-3 mmol	SI p004 / S4 · Synthesis of NU-4000
Metal Source	CuCl2	3.00 mg; 22.3 x 10-3 mmol	SI p004 / S4 · Synthesis of NU-4000
Solvent	DMF	200 uL	SI p004 / S4 · Synthesis of NU-4000
Solvent	toluene	250 uL	SI p004 / S4 · Synthesis of NU-4000
Solvent	H2O	50 uL	SI p004 / S4 · Synthesis of NU-4000

Complete recipeSource: Both

Route 2: Solvothermal

SI p004 / S4 · Synthesis of NU-4001

Metal precursorsCuCl2 (3.00 mg, 22.3 x 10-3 mmol)

Linker precursorsH6L (2.00 mg, 2.10 x 10-3 mmol)

SolventsDMF (400 uL), toluene (250 uL), H2O (75 uL)

Atmospheresealed 1.5-dram vial; atmosphere not otherwise specified

Temperature100

Time12

Work-upAfter cooling, crystals collected by centrifugation; washed with DMF (5 mL x 3) and acetone (5 mL x 3); soaked in acetone overnight; washed with acetone three more times.

Activation60 C overnight under dynamic vacuum on Micromeritics Smart VacPrep instrument or supercritical CO2

Scalability contextmilligram-scale vial synthesis; no scale-up demonstrated

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H6L	2.00 mg; 2.10 x 10-3 mmol	SI p004 / S4 · Synthesis of NU-4001
Metal Source	CuCl2	3.00 mg; 22.3 x 10-3 mmol	SI p004 / S4 · Synthesis of NU-4001
Solvent	DMF	400 uL	SI p004 / S4 · Synthesis of NU-4001
Solvent	toluene	250 uL	SI p004 / S4 · Synthesis of NU-4001
Solvent	H2O	75 uL	SI p004 / S4 · Synthesis of NU-4001

Complete recipeSource: Both

Route 3: Solvothermal

SI p004-p005 / S4-S5 · Synthesis of NU-4002

Metal precursorsCuCl2 (3.00 mg, 22.3 x 10-3 mmol)

Linker precursorsH6L (2.00 mg, 2.10 x 10-3 mmol)

SolventsDMF (300 uL), toluene (250 uL), H2O (75 uL)

Atmospheresealed 1.5-dram vial; atmosphere not otherwise specified

Temperature100

Time12

Work-upAfter cooling, crystals collected by centrifugation; washed with DMF (5 mL x 3) and acetone (5 mL x 3); soaked in acetone overnight; washed with acetone three more times.

Activation60 C overnight under dynamic vacuum on Micromeritics Smart VacPrep instrument or supercritical CO2

Scalability contextmilligram-scale vial synthesis; no scale-up demonstrated

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H6L	2.00 mg; 2.10 x 10-3 mmol	SI p004-p005 / S4-S5 · Synthesis of NU-4002
Metal Source	CuCl2	3.00 mg; 22.3 x 10-3 mmol	SI p004-p005 / S4-S5 · Synthesis of NU-4002
Solvent	DMF	300 uL	SI p004-p005 / S4-S5 · Synthesis of NU-4002
Solvent	toluene	250 uL	SI p004-p005 / S4-S5 · Synthesis of NU-4002
Solvent	H2O	75 uL	SI p004-p005 / S4-S5 · Synthesis of NU-4002

Complete recipeSource: Both

Route 4: Solvothermal

SI p005 / S5 · Synthesis of NU-4003

Metal precursorsCuCl2 (3.00 mg, 22.3 x 10-3 mmol)

Linker precursorsH6L (2.00 mg, 2.10 x 10-3 mmol)

SolventsDMF (250 uL), toluene (250 uL), H2O (75 uL)

Atmospheresealed 1.5-dram vial; atmosphere not otherwise specified

Temperature100

Time12

Work-upAfter cooling, crystals collected by centrifugation; washed with DMF (5 mL x 3) and acetone (5 mL x 3); soaked in acetone overnight; washed with acetone three more times.

Activation80 C overnight under dynamic vacuum on Micromeritics Smart VacPrep instrument

Scalability contextmilligram-scale vial synthesis; no scale-up demonstrated

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H6L	2.00 mg; 2.10 x 10-3 mmol	SI p005 / S5 · Synthesis of NU-4003
Metal Source	CuCl2	3.00 mg; 22.3 x 10-3 mmol	SI p005 / S5 · Synthesis of NU-4003
Solvent	DMF	250 uL	SI p005 / S5 · Synthesis of NU-4003
Solvent	toluene	250 uL	SI p005 / S5 · Synthesis of NU-4003
Solvent	H2O	75 uL	SI p005 / S5 · Synthesis of NU-4003

Complete recipeSource: Both

Route 5: Solvothermal

SI p005 / S5 · Synthesis of NU-4003-C60 with different loading

Metal precursorsCuCl2 (3.00 mg, 22.3 x 10-3 mmol)

Linker precursorsH6L (2.00 mg, 2.10 x 10-3 mmol)

Solventssame as NU-4003-C60: DMF (250 uL), toluene (250 uL), H2O (75 uL)

Additivesfullerene C60 (0.8 mg)

Atmospheresealed 1.5-dram vial; atmosphere not otherwise specified

Temperature100

Time12

Work-upAfter cooling, crystals collected by centrifugation; washed with toluene multiple times (5 mL each, until colourless), then DMF (5 mL x 3) and acetone (5 mL x 3); soaked in acetone overnight; washed with acetone three more times.

Activation80 C overnight under dynamic vacuum, following NU-4003-C60 workup

Scalability contextmilligram-scale vial synthesis; no scale-up demonstrated

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H6L	2.00 mg; 2.10 x 10-3 mmol	SI p005 / S5 · Synthesis of NU-4003-C60 with different loading
Metal Source	CuCl2	3.00 mg; 22.3 x 10-3 mmol	SI p005 / S5 · Synthesis of NU-4003-C60 with different loading
Additive	fullerene C60	0.8 mg	SI p005 / S5 · Synthesis of NU-4003-C60 with different loading

Complete recipeSource: Both

Route 6: Solvothermal

SI p005 / S5 · Synthesis of NU-4003-C60 with different loading

Metal precursorsCuCl2 (3.00 mg, 22.3 x 10-3 mmol)

Linker precursorsH6L (2.00 mg, 2.10 x 10-3 mmol)

Solventssame as NU-4003-C60: DMF (250 uL), toluene (250 uL), H2O (75 uL)

Additivesfullerene C60 (1.00 mg)

Atmospheresealed 1.5-dram vial; atmosphere not otherwise specified

Temperature100

Time12

Activation80 C overnight under dynamic vacuum, following NU-4003-C60 workup

Scalability contextmilligram-scale vial synthesis; no scale-up demonstrated

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H6L	2.00 mg; 2.10 x 10-3 mmol	SI p005 / S5 · Synthesis of NU-4003-C60 with different loading
Metal Source	CuCl2	3.00 mg; 22.3 x 10-3 mmol	SI p005 / S5 · Synthesis of NU-4003-C60 with different loading
Additive	fullerene C60	1.00 mg	SI p005 / S5 · Synthesis of NU-4003-C60 with different loading

Complete recipeSource: Both

Route 7: Solvothermal

SI p005 / S5 · Synthesis of NU-4003-C60 with different loading

Metal precursorsCuCl2 (3.00 mg, 22.3 x 10-3 mmol)

Linker precursorsH6L (2.00 mg, 2.10 x 10-3 mmol)

Solventssame as NU-4003-C60: DMF (250 uL), toluene (250 uL), H2O (75 uL)

Additivesfullerene C60 (2.00 mg)

Atmospheresealed 1.5-dram vial; atmosphere not otherwise specified

Temperature100

Time12

Activation80 C overnight under dynamic vacuum, following NU-4003-C60 workup

Scalability contextmilligram-scale vial synthesis; no scale-up demonstrated

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H6L	2.00 mg; 2.10 x 10-3 mmol	SI p005 / S5 · Synthesis of NU-4003-C60 with different loading
Metal Source	CuCl2	3.00 mg; 22.3 x 10-3 mmol	SI p005 / S5 · Synthesis of NU-4003-C60 with different loading
Additive	fullerene C60	2.00 mg	SI p005 / S5 · Synthesis of NU-4003-C60 with different loading

Complete recipeSource: Both

Route 8: Solvothermal

SI p005 / S5 · Synthesis of NU-4003-C60

Metal precursorsCuCl2 (3.00 mg, 22.3 x 10-3 mmol)

Linker precursorsH6L (2.00 mg, 2.10 x 10-3 mmol)

SolventsDMF (250 uL), toluene (250 uL), H2O (75 uL)

Additivesfullerene C60 (4.00 mg, 5.55 x 10-3 mmol)

Atmospheresealed 1.5-dram vial; atmosphere not otherwise specified

Temperature100

Time12

Activation80 C overnight under dynamic vacuum on Micromeritics Smart VacPrep instrument

Scalability contextmilligram-scale vial synthesis; no scale-up demonstrated

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H6L	2.00 mg; 2.10 x 10-3 mmol	SI p005 / S5 · Synthesis of NU-4003-C60
Metal Source	CuCl2	3.00 mg; 22.3 x 10-3 mmol	SI p005 / S5 · Synthesis of NU-4003-C60
Additive	fullerene C60	4.00 mg; 5.55 x 10-3 mmol	SI p005 / S5 · Synthesis of NU-4003-C60
Solvent	DMF	250 uL	SI p005 / S5 · Synthesis of NU-4003-C60
Solvent	toluene	250 uL	SI p005 / S5 · Synthesis of NU-4003-C60
Solvent	H2O	75 uL	SI p005 / S5 · Synthesis of NU-4003-C60