Synthesis · Tuning the Structure-Property Relationships of Metallophthalocyanine-Based Two-Dimensional Conductive Metal-Organic Frameworks with Different Metal Linkages

4 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 p.15-16 · Section S2 Synthetic procedures · Table S2

Metal precursorsAnhydrous copper(II) acetate (9.08 mg, 2.5 eq.)

Linker precursorsCuPc(OH)8 (14.1 mg, 0.02 mmol; 4 mM ligand concentration)

SolventsDMSO (4 mL)

AdditivesNone in optimised condition

AtmosphereFlask loosely capped to permit exposure to air

Temperature85

Time20

Oxidant / reductantAir exposure; acetate acts as base/modulator according to authors

Work-upCool to room temperature; isolate precipitate by centrifuge; wash with DMF, H2O, MeOH and acetone, each 3 x 20 mL.

ActivationDried in vacuum oven at 50 deg C for 12 h; BET samples further degassed under vacuum at 100 deg C for 18 h.

Scalability contextSmall-batch synthesis gave 14.6 mg black solid from 14.1 mg CuPc(OH)8.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	CuPc(OH)8	14.1 mg, 0.02 mmol · 4 mM	SI p.15-16 · Section S2 Synthetic procedures · Table S2
Solvent	DMSO	4 mL	SI p.15-16 · Section S2 Synthetic procedures · Table S2
Metal Source	Anhydrous copper(II) acetate	9.08 mg, 2.5 eq.	SI p.15-16 · Section S2 Synthetic procedures · Table S2

Complete recipeSource: Both

Route 2: Solvothermal

SI p.11-13 · Section S2 Synthetic procedures · Table S1

Metal precursorsNickel acetate tetrahydrate (12.44 mg, 2.5 eq.)

Linker precursorsCuPc(OH)8 (14.1 mg, 0.02 mmol; 8 mM ligand concentration)

SolventsDMF/H2O (2 mL/6 mL) plus metal salt in H2O (2 mL)

AdditivesNH4OH (28-30%, 2 mL; concentrated NH4OH, 20 vol%)

AtmosphereFlask loosely capped to permit exposure to air

Temperature85

Time18

Oxidant / reductantAir exposure; ammonium hydroxide base additive

Work-upCool to room temperature; isolate precipitate by centrifugation; wash with DMF, H2O, MeOH and acetone, each 3 x 20 mL.

ActivationDried in vacuum oven at 50 deg C for 12 h; BET samples further degassed under vacuum at 100 deg C for 18 h.

Scalability contextSmall-batch synthesis gave 14.9 mg black solid from 14.1 mg CuPc(OH)8.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	CuPc(OH)8	14.1 mg, 0.02 mmol · 8 mM	SI p.11-13 · Section S2 Synthetic procedures · Table S1
Solvent	DMF/H2O	2 mL/6 mL · 1:4 v/v in Table S1	SI p.11-13 · Section S2 Synthetic procedures · Table S1
Base	NH4OH	2 mL · 28-30%; 20 vol%	SI p.11-13 · Section S2 Synthetic procedures · Table S1
Metal Source	Nickel acetate tetrahydrate	12.44 mg, 2.5 eq. · in H2O (2 mL)	SI p.11-13 · Section S2 Synthetic procedures · Table S1

Complete recipeSource: Both

Route 3: Solvothermal

SI p.18-20 · Section S2 Synthetic procedures · Table S3

Metal precursorsZinc(II) acetate dihydrate (10.97 mg, 2.5 eq.)

Linker precursorsCuPc(OH)8 (14.1 mg, 0.02 mmol; 8 mM ligand concentration)

SolventsDMF/H2O (2 mL/6 mL) plus metal salt in H2O (2 mL)

AdditivesNH4OH (28-30%, 2 mL; concentrated NH4OH, 20 vol%)

AtmosphereFlask loosely capped to permit exposure to air

Temperature85

Time18

Oxidant / reductantAir exposure; ammonium hydroxide base additive

Work-upCool to room temperature; isolate precipitate by centrifuge; wash with DMF, H2O, MeOH and acetone, each 3 x 20 mL.

ActivationDried in vacuum oven at 50 deg C for 12 h; BET samples further degassed under vacuum at 100 deg C for 18 h.

Scalability contextSmall-batch synthesis gave 15.4 mg black solid from 14.1 mg CuPc(OH)8.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	CuPc(OH)8	14.1 mg, 0.02 mmol · 8 mM	SI p.18-20 · Section S2 Synthetic procedures · Table S3
Solvent	DMF/H2O	2 mL/6 mL · 1:4 v/v in Table S3	SI p.18-20 · Section S2 Synthetic procedures · Table S3
Metal Source	zinc(II) acetate dihydrate	10.97 mg, 2.5 eq. · in H2O (2 mL)	SI p.18-20 · Section S2 Synthetic procedures · Table S3
Base	NH4OH	2 mL · 28-30%; 20 vol%	SI p.18-20 · Section S2 Synthetic procedures · Table S3

Complete recipeSource: SI

Route 4: Other

SI p.6-10 · Section S2 Synthetic procedures · Scheme S1

Metal precursorsCopper chloride dihydrate in CuPc(OMe)8 formation; CuPc(OMe)8 already contains Cu for demethylation step

Linker precursors4,5-dibromoveratrole -> 4,5-dimethoxyphthalodinitrile -> CuPc(OMe)8 -> CuPc(OH)8

SolventsAnhydrous DMF; anhydrous ethylene glycol; anhydrous DCM; methanol; water; diethyl ether Soxhlet extraction

AdditivesCopper(I) cyanide, concentrated ammonium hydroxide, urea, 1% ammonium molybdate, BBr3

AtmosphereAir led through ammonium hydroxide workup for first step; N2 evacuation-refill cycles and N2 atmosphere for BBr3 demethylation

Temperature160; 180; room temperature; drying at 65, 60 and 50

Time5 h reflux; 12 h air bubbling; 3 days Soxhlet; 4 days reflux; 5 days BBr3 demethylation

Oxidant / reductantBBr3 demethylation reagent; air during ammonium hydroxide workup

Work-upFiltered/washed with dilute ammonium hydroxide and water, Soxhlet extracted with ether, recrystallised with MeOH; CuPc(OMe)8 centrifuged and washed with DI water/methanol; CuPc(OH)8 quenched with methanol, centrifuged, washed with MeOH and acetone.

ActivationDried under reduced pressure at 65, 60, or 50 deg C depending on step.

Scalability contextPrecursor was prepared on gram scale: 12.2 g phthalodinitrile, 1.05 g CuPc(OMe)8, 0.65 g CuPc(OH)8 reported.

Show 10 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	4,5-dibromoveratrole	30.0 g, 1.014 mol	SI p.6-10 · Section S2 Synthetic procedures · Scheme S1
Additive	copper cyanide	27.24 g, 3 eq	SI p.6-10 · Section S2 Synthetic procedures · Scheme S1
Solvent	anhydrous DMF	380 mL	SI p.6-10 · Section S2 Synthetic procedures · Scheme S1
Base	concentrated ammonium hydroxide solution	1200 mL	SI p.6-10 · Section S2 Synthetic procedures · Scheme S1
Metal Source	copper chloride dihydrate	0.4328 g, 0.25 eq	SI p.6-10 · Section S2 Synthetic procedures · Scheme S1
Solvent	anhydrous ethylene glycol	60 mL	SI p.6-10 · Section S2 Synthetic procedures · Scheme S1
Additive	urea	0.601 g, 10 mmol	SI p.6-10 · Section S2 Synthetic procedures · Scheme S1
Additive	1% ammonium molybdate	0.235 g · 1%	SI p.6-10 · Section S2 Synthetic procedures · Scheme S1
Reductant	BBr3	4.65 mL, 40 eq	SI p.6-10 · Section S2 Synthetic procedures · Scheme S1
Solvent	anhydrous dichloromethane	50 mL	SI p.6-10 · Section S2 Synthetic procedures · Scheme S1