Synthesis · Effective visible-light CO2 photoreduction over (metallo)porphyrin-based metal–organic frameworks to achieve useful hydrocarbons

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

S2.1. Synthesis procedure of metalloporphyrinic linker

Metal precursorsMCl2,nH2O (M = Fe, Co, Ni and Cu), 12.8 mmol for metallation step

Linker precursorsTPPCOOMe prepared from P-formylbenzoat (42 mmol, 6900 mg) and pyrrole (43 mmol, 3 mL); hydrolysed to MTCPP

Solventspropionic acid (100 mL); DMF (100 mL); H2O (150 mL plus 25 mL for KOH solution); chloroform; teterahydrofuran (25 mL); methanol (25 mL); distilled water

AdditivesKOH (46 mmol, 2.630 mg as reported); HCl (1 M); magnesium sulfate; methanol, ethyl acetate and THF washes; HCl wash for Fe-TPPCOOMe and Ni-TPPCOOMe

Atmospherenot specified

Temperaturereflux; room-temperature cooling/drying; no explicit temperatures reported

Time12 h reflux for TPPCOOMe; 6 h reflux for M-TPPCOOMe; overnight room-temperature drying; 12 h reflux for hydrolysis

Oxidant / reductantKOH hydrolysis followed by acidification with HCl; no separate redox reagent specified

Work-upTPPCOOMe filtered and washed 3 times with methanol, ethyl acetate and THF; metallated precipitate filtered, washed with H2O, dried, extracted into chloroform, washed with water/HCl as specified, dried over magnesium sulfate and solvent evaporated; MTCPP precipitate collected and washed with water

ActivationMTCPP dried under vacuum

Scalability contextNo scale-up discussion; gram/millimole-scale precursor amounts are reported.

Show 10 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	P-formylbenzoat	42 mmol; 6900 mg	S2.1. Synthesis procedure of metalloporphyrinic linker
Linker	pyrrole	43 mmol; 3 mL	S2.1. Synthesis procedure of metalloporphyrinic linker
Solvent	propionic acid	100 mL	S2.1. Synthesis procedure of metalloporphyrinic linker
Linker	TPPCOOMe	1 mmol; 854 mg	S2.1. Synthesis procedure of metalloporphyrinic linker
Metal Source	MCl2,nH2O (M= Fe, Co, Ni and Cu)	12.8 mmol	S2.1. Synthesis procedure of metalloporphyrinic linker
Solvent	DMF	100 mL	S2.1. Synthesis procedure of metalloporphyrinic linker
Base	KOH	46 mmol; 2.630 mg	S2.1. Synthesis procedure of metalloporphyrinic linker
Acid	HCl	1 M	S2.1. Synthesis procedure of metalloporphyrinic linker
Solvent	teterahydrofuran	25 mL	S2.1. Synthesis procedure of metalloporphyrinic linker
Solvent	methanol	25 mL	S2.1. Synthesis procedure of metalloporphyrinic linker

Partial recipeSource: Both

Route 2: Solvothermal

S2.2. Synthesis and activation of PCN-222 (M)

Metal precursorsZrCl4 (75 mg); CoTCPP / MTCPP (50 mg, M = Co)

Linker precursorsMTCPP metalloporphyrinic linker (M = Co), 50 mg

SolventsDMF (8 mL for synthesis; 40 mL for purification reflux); acetone for washing and solvent exchange

Additivesbenzoic acid (2700 mg)

Atmospherenot specified

TemperatureDMF reflux; final vacuum drying at 120 C

Time24 h synthesis reflux; 12 h DMF purification reflux; 24 h acetone stirring; 6 h vacuum drying

Oxidant / reductantnone specified

Work-upcool to room temperature; collect coloured needle-shaped MOF; wash by DMF; reflux in 40 mL DMF for 12 h to remove unreacted starting material and impurities; wash by DMF and acetone; stir in fresh acetone for 24 h

Activationdried under vacuum at 120 C for 6 h

Scalability contextSingle batch using 75 mg ZrCl4 and 50 mg linker; no scale-up discussion.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	75 mg	S2.2. Synthesis and activation of PCN-222 (M)
Linker	MTCPP (M = Co)	50 mg	S2.2. Synthesis and activation of PCN-222 (M)
Additive	benzoic acid	2700 mg	S2.2. Synthesis and activation of PCN-222 (M)
Solvent	DMF	8 mL synthesis; 40 mL purification	S2.2. Synthesis and activation of PCN-222 (M)
Solvent	acetone	fresh acetone for 24 h stirring	S2.2. Synthesis and activation of PCN-222 (M)

Partial recipeSource: Both

Route 3: Solvothermal

S2.2. Synthesis and activation of PCN-222 (M)

Metal precursorsZrCl4 (75 mg); CuTCPP / MTCPP (50 mg, M = Cu)

Linker precursorsMTCPP metalloporphyrinic linker (M = Cu), 50 mg

SolventsDMF (8 mL for synthesis; 40 mL for purification reflux); acetone for washing and solvent exchange

Additivesbenzoic acid (2700 mg)

Atmospherenot specified

TemperatureDMF reflux; final vacuum drying at 120 C

Time24 h synthesis reflux; 12 h DMF purification reflux; 24 h acetone stirring; 6 h vacuum drying

Oxidant / reductantnone specified

Activationdried under vacuum at 120 C for 6 h

Scalability contextSingle batch using 75 mg ZrCl4 and 50 mg linker; no scale-up discussion.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	75 mg	S2.2. Synthesis and activation of PCN-222 (M)
Linker	MTCPP (M = Cu)	50 mg	S2.2. Synthesis and activation of PCN-222 (M)
Additive	benzoic acid	2700 mg	S2.2. Synthesis and activation of PCN-222 (M)
Solvent	DMF	8 mL synthesis; 40 mL purification	S2.2. Synthesis and activation of PCN-222 (M)
Solvent	acetone	fresh acetone for 24 h stirring	S2.2. Synthesis and activation of PCN-222 (M)

Partial recipeSource: Both

Route 4: Solvothermal

S2.2. Synthesis and activation of PCN-222 (M)

Metal precursorsZrCl4 (75 mg); FeTCPP / MTCPP (50 mg, M = Fe)

Linker precursorsMTCPP metalloporphyrinic linker (M = Fe), 50 mg

SolventsDMF (8 mL for synthesis; 40 mL for purification reflux); acetone for washing and solvent exchange

Additivesbenzoic acid (2700 mg)

Atmospherenot specified

TemperatureDMF reflux; final vacuum drying at 120 C

Time24 h synthesis reflux; 12 h DMF purification reflux; 24 h acetone stirring; 6 h vacuum drying

Oxidant / reductantnone specified

Activationdried under vacuum at 120 C for 6 h

Scalability contextSingle batch using 75 mg ZrCl4 and 50 mg linker; no scale-up discussion.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	75 mg	S2.2. Synthesis and activation of PCN-222 (M)
Linker	MTCPP (M = Fe)	50 mg	S2.2. Synthesis and activation of PCN-222 (M)
Additive	benzoic acid	2700 mg	S2.2. Synthesis and activation of PCN-222 (M)
Solvent	DMF	8 mL synthesis; 40 mL purification	S2.2. Synthesis and activation of PCN-222 (M)
Solvent	acetone	fresh acetone for 24 h stirring	S2.2. Synthesis and activation of PCN-222 (M)

Partial recipeSource: Both

Route 5: Solvothermal

S2.2. Synthesis and activation of PCN-222 (M)

Metal precursorsZrCl4 (75 mg); NiTCPP / MTCPP (50 mg, M = Ni)

Linker precursorsMTCPP metalloporphyrinic linker (M = Ni), 50 mg

SolventsDMF (8 mL for synthesis; 40 mL for purification reflux); acetone for washing and solvent exchange

Additivesbenzoic acid (2700 mg)

Atmospherenot specified

TemperatureDMF reflux; final vacuum drying at 120 C

Time24 h synthesis reflux; 12 h DMF purification reflux; 24 h acetone stirring; 6 h vacuum drying

Oxidant / reductantnone specified

Activationdried under vacuum at 120 C for 6 h

Scalability contextSingle batch using 75 mg ZrCl4 and 50 mg linker; no scale-up discussion.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	75 mg	S2.2. Synthesis and activation of PCN-222 (M)
Linker	MTCPP (M = Ni)	50 mg	S2.2. Synthesis and activation of PCN-222 (M)
Additive	benzoic acid	2700 mg	S2.2. Synthesis and activation of PCN-222 (M)
Solvent	DMF	8 mL synthesis; 40 mL purification	S2.2. Synthesis and activation of PCN-222 (M)
Solvent	acetone	fresh acetone for 24 h stirring	S2.2. Synthesis and activation of PCN-222 (M)

Vague recipeSource: Main

Route 6: Unknown

2 · Photocatalytic reaction

Metal precursorsZr source not specified for nonmetal PCN-222 control

Linker precursorsnonmetal porphyrinic PCN-222 linker presumed H2TCPP/TCPP, exact source not specified

Solventsnot specified for nonmetal PCN-222 control

Additivesnot specified for nonmetal PCN-222 control

Atmospherenot specified

Temperaturenot specified

Timenot specified

Work-upnot specified

Activationnot specified

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zr source not specified	Not specified	2 · Photocatalytic reaction
Linker	nonmetal porphyrinic linker not specified	Not specified	2 · Photocatalytic reaction