Synthesis · A simplistic approach for the synthesis of Covalent Organic Frameworks(COFs) comprising of tetrafunctionalized porphyrin and polyoxometalates to uncover catalytic applications

6 structured synthesis routes

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

Partial recipeSource: SI

Route 1: Other

SI text · Experimental Details; Synthesis of P@4OOMe-Zn

Metal precursorsZn(OAc)2.2H2O (0.01 g, 1 eq.)

Linker precursorsP@4OOMe2 (0.036 g, 1 eq.)

SolventsMethanol (70 mL); dichloromethane (60 mL initially, then 100 mL DCM for workup)

AdditivesConcentrated aqueous K2CO3 wash

AtmosphereAmbient atmosphere not otherwise specified.

Temperatureambient

Time3.5

Work-upRemoved solvent by rotary evaporator; dried; dissolved in 100 mL DCM; washed three times with 100 mL distilled water and 100 mL concentrated aqueous K2CO3 solution.

ActivationDried after rotary evaporation; no separate activation reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(OAc)2.2H2O	0.01 g, 1 eq.	SI text · Experimental Details; Synthesis of P@4OOMe-Zn
Linker	P@4OOMe2	0.036 g, 1 eq.	SI text · Experimental Details; Synthesis of P@4OOMe-Zn
Solvent	Methanol	70 mL	SI text · Experimental Details; Synthesis of P@4OOMe-Zn
Solvent	Dichloromethane	60 mL initially; 100 mL for workup	SI text · Experimental Details; Synthesis of P@4OOMe-Zn
Base	Concentrated aqueous K2CO3 solution	100 mL wash	SI text · Experimental Details; Synthesis of P@4OOMe-Zn

Partial recipeSource: Both

Route 2: Solvothermal

main p.3 · 2.2. Synthesis of P@M-And COF · Scheme 1

Metal precursorsalpha-Anderson POM (0.3 g, 4 eq.); Cu(CH3COO)2.H2O (0.02 g, 4 eq.)

Linker precursorsTris@ZnP (0.05 g, 1 eq.)

SolventsDried DMAC (2-3 mL)

AtmosphereNitrogen; protected from light using aluminium foil.

Temperature85 then 120

Time48 then 48

Work-upSame workup as P@Ni-AndCOF: cooled, autoclaved, poured into chilled water, centrifuged, washed/dried.

ActivationDried completely and in vacuum desiccator by analogy to P@Ni-AndCOF.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	alpha-Anderson POM	0.3 g, 4 eq.	main p.3 · 2.2. Synthesis of P@M-And COF · Scheme 1
Metal Source	Cu(CH3COO)2.H2O	0.02 g, 4 eq.	main p.3 · 2.2. Synthesis of P@M-And COF · Scheme 1
Linker	Tris@ZnP	0.05 g, 1 eq.	main p.3 · 2.2. Synthesis of P@M-And COF · Scheme 1
Solvent	Dried DMAC	2-3 mL	main p.3 · 2.2. Synthesis of P@M-And COF · Scheme 1
Other	Chilled distilled water	Not specified	main p.3 · 2.2. Synthesis of P@M-And COF · Scheme 1
Other	Ether wash	Not specified	main p.3 · 2.2. Synthesis of P@M-And COF · Scheme 1

Partial recipeSource: Both

Route 3: Drop Cast

main p.3-4 · 2.3. Fabrication of thin films

SolventsDMF for P@Cu-AndCOF coating; ethylene glycol for electrolyte.

AdditivesTiO2 (0.5 g), vinegar, iodine (127 mg), KI (830 mg), carbon black counter electrode.

AtmosphereAmbient during electrode fabrication; synthesis route does not specify inert atmosphere.

Temperatureup to 200 for TiO2 paste drying; oven drying at solvent boiling point

Time1 h for TiO2 drying

Substrate orientationConducting side of ITO electrode coated with TiO2/vinegar paste, then P@Cu-AndCOF solution spread on top.

Oxidant / reductantI-/I3- electrolyte from iodine and KI in ethylene glycol.

Work-upAssembled dry ITO electrode with electrolyte and carbon-black counter electrode.

ActivationOven drying after coating.

Show 8 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	Titanium dioxide	0.5 g	main p.3-4 · 2.3. Fabrication of thin films
Acid	Vinegar	very small amount	main p.3-4 · 2.3. Fabrication of thin films
Solvent	DMF	concentrated P@Cu-AndCOF solution	main p.3-4 · 2.3. Fabrication of thin films
Electrolyte	Iodine	127 mg	main p.3-4 · 2.3. Fabrication of thin films
Electrolyte	KI	830 mg	main p.3-4 · 2.3. Fabrication of thin films
Solvent	Ethylene glycol	10 mL	main p.3-4 · 2.3. Fabrication of thin films
Other	ITO electrode	Not specified	main p.3-4 · 2.3. Fabrication of thin films
Other	Carbon black counter electrode	Not specified	main p.3-4 · 2.3. Fabrication of thin films

Partial recipeSource: Both

Route 4: Solvothermal

main p.2-3 · 2.2. Synthesis of P@M-And COF · Scheme 1

Metal precursorsalpha-Anderson POM (0.3 g, 4 eq.); Ni(CH3COO)2.4H2O (0.035 g, 4 eq.)

Linker precursorsTris@ZnP (0.05 g, 1 eq.)

SolventsDried DMAC (2-3 mL)

AtmosphereNitrogen; protected from light using aluminium foil.

Temperature85 then 120

Time48 then 48

Work-upCooled; transferred to Teflon autoclave for oven step; resulting solid poured into chilled distilled water, collected by centrifugation, washed with ether.

ActivationDried completely, then dried in vacuum desiccator.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	alpha-Anderson POM	0.3 g, 4 eq.	main p.2-3 · 2.2. Synthesis of P@M-And COF · Scheme 1
Metal Source	Ni(CH3COO)2.4H2O	0.035 g, 4 eq.	main p.2-3 · 2.2. Synthesis of P@M-And COF · Scheme 1
Linker	Tris@ZnP	0.05 g, 1 eq.	main p.2-3 · 2.2. Synthesis of P@M-And COF · Scheme 1
Solvent	Dried DMAC	2-3 mL	main p.2-3 · 2.2. Synthesis of P@M-And COF · Scheme 1
Other	Chilled distilled water	Not specified	main p.2-3 · 2.2. Synthesis of P@M-And COF · Scheme 1
Other	Ether wash	Not specified	main p.2-3 · 2.2. Synthesis of P@M-And COF · Scheme 1

Partial recipeSource: Both

Route 5: Drop Cast

main p.3-4 · 2.3. Fabrication of thin films

SolventsDMF for P@Ni-AndCOF coating; ethylene glycol for electrolyte.

AdditivesTiO2 (0.5 g), vinegar, iodine (127 mg), KI (830 mg), carbon black counter electrode.

AtmosphereAmbient during electrode fabrication; synthesis route does not specify inert atmosphere.

Temperatureup to 200 for TiO2 paste drying; oven drying at solvent boiling point

Time1 h for TiO2 drying

Substrate orientationConducting side of ITO electrode coated with TiO2/vinegar paste, then P@Ni-AndCOF solution spread on top.

Oxidant / reductantI-/I3- electrolyte from iodine and KI in ethylene glycol.

Work-upAssembled dry ITO electrode with electrolyte and carbon-black counter electrode.

ActivationOven drying after coating.

Show 8 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	Titanium dioxide	0.5 g	main p.3-4 · 2.3. Fabrication of thin films
Acid	Vinegar	very small amount	main p.3-4 · 2.3. Fabrication of thin films
Solvent	DMF	concentrated P@Ni-AndCOF solution	main p.3-4 · 2.3. Fabrication of thin films
Electrolyte	Iodine	127 mg	main p.3-4 · 2.3. Fabrication of thin films
Electrolyte	KI	830 mg	main p.3-4 · 2.3. Fabrication of thin films
Solvent	Ethylene glycol	10 mL	main p.3-4 · 2.3. Fabrication of thin films
Other	ITO electrode	Not specified	main p.3-4 · 2.3. Fabrication of thin films
Other	Carbon black counter electrode	Not specified	main p.3-4 · 2.3. Fabrication of thin films

Partial recipeSource: Both

Route 6: Other

main p.2 · 2.1. Synthesis of Tris@ZnP

Metal precursorsP@4OOMe-Zn (0.1 g, 1 eq.)

Linker precursorsTris(hydroxymethyl)aminomethane (THMAM, 0.05 g, 4 eq.)

SolventsDried DMSO (2-3 mL)

AdditivesK2CO3 (0.05 g, 4 eq.)

AtmosphereNitrogen; protected from light.

Temperature85

Time17

Work-upCooled to room temperature, poured dropwise into 100 mL chilled distilled water, centrifuged.

ActivationDried in vacuum.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	P@4OOMe-Zn	0.1 g, 1 eq.	main p.2 · 2.1. Synthesis of Tris@ZnP
Base	K2CO3	0.05 g, 4 eq.	main p.2 · 2.1. Synthesis of Tris@ZnP
Linker	Trishydroxy-methylamino methane / THMAM	0.05 g, 4 eq.	main p.2 · 2.1. Synthesis of Tris@ZnP
Solvent	Dried DMSO	2-3 mL	main p.2 · 2.1. Synthesis of Tris@ZnP
Other	Distilled water, chilled	100 mL	main p.2 · 2.1. Synthesis of Tris@ZnP