cMOF Evidence Base

Synthesis evidence

Large π-Conjugated Metal-Organic Frameworks for Infrared-Light-Driven CO2Reduction

Zeng J.-Y., Wang X.-S., Xie B.-R. et al. · Journal of the American Chemical Society · 2022 · 1218-1231

5 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

S15 · Section 2 Design and synthesis of MOFs · Figure S7

Metal precursorsZrCl4 (10 mg, 0.0429 mmol)
Linker precursorsTBCP linker (13.5 mg, 0.0123 mmol)
Solvents2 mL DMF in detailed SI; main general method states DEF
Additivesbenzoic acid (200 mg, 1.64 mmol)
Atmospheredegassed by three freeze-pump-thaw cycles; flame sealed under vacuum
Temperature120
Time24
Oxidant / reductantnone for MOF assembly
Work-upyielded dark green cubic crystals; 75% yield based on organic linkers; gram scale obtained by combining products from multiple Pyrex tube reactions
ActivationMain general method: methanol exchange five times in 3 days; porosity activation: DMF wash 3 days, acetone exchange 1 day, 120 °C vacuum 6 h; photocatalysis activation: acetonitrile exchange five times in 3 days.
Scalability contextGram scale obtained by combining products from multiple Pyrex tube reactions.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZrCl4(10 mg, 0.0429 mmol)S15 · Section 2 Design and synthesis of MOFs · Figure S7
LinkerTBCP linker(13.5 mg, 0.0123 mmol)S15 · Section 2 Design and synthesis of MOFs · Figure S7
Solvent2 mL DMF in detailed SI; main general method states DEFNot specifiedS15 · Section 2 Design and synthesis of MOFs · Figure S7
Additivebenzoic acid(200 mg, 1.64 mmol)S15 · Section 2 Design and synthesis of MOFs · Figure S7
Complete recipeSource: Both

Route 2: Solvothermal

S16 · Section 2 Design and synthesis of MOFs · Figure S8

Metal precursorsZrCl4 (7.4 mg, 0.0314 mmol)
Linker precursorsTBML (8.2 mg, 0.00626 mmol)
SolventsDEF (1.0 mL)
Additivesbenzoic acid (270 mg, 2.214 mmol)
Atmospheredegassed by three freeze-pump-thaw cycles; flame sealed under vacuum
Temperature120
Time24
Oxidant / reductantnone for MOF assembly
Work-upyielded dark green cubic crystals; 68% yield based on organic ligand; gram scale obtained by combining products from multiple Pyrex tube reactions
ActivationMain general method: methanol exchange five times in 3 days; porosity activation: DMF wash 3 days, acetone exchange 1 day, 120 °C vacuum 6 h; photocatalysis activation: acetonitrile exchange five times in 3 days.
Scalability contextGram scale obtained by combining products from multiple Pyrex tube reactions.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZrCl4(7.4 mg, 0.0314 mmol)S16 · Section 2 Design and synthesis of MOFs · Figure S8
LinkerTBML(8.2 mg, 0.00626 mmol)S16 · Section 2 Design and synthesis of MOFs · Figure S8
SolventDEF (1.0 mL)Not specifiedS16 · Section 2 Design and synthesis of MOFs · Figure S8
Additivebenzoic acid(270 mg, 2.214 mmol)S16 · Section 2 Design and synthesis of MOFs · Figure S8
Complete recipeSource: Both

Route 3: Solvothermal

S17 · Section 2 Design and synthesis of MOFs · Figure S9

Metal precursorsZrCl4 (7.4 mg, 0.0318 mmol)
Linker precursorsTML (8.2 mg, 0.00634 mmol)
SolventsDEF (1.0 mL)
Additivesbenzoic acid (270 mg, 2.214 mmol)
Atmospheredegassed by three freeze-pump-thaw cycles; flame sealed under vacuum
Temperature120
Time24
Oxidant / reductantnone for MOF assembly
Work-upyielded dark green cubic crystals; 45% yield based on organic ligand; gram scale obtained by combining products from multiple Pyrex tube reactions
ActivationMain general method: methanol exchange five times in 3 days; porosity activation: DMF wash 3 days, acetone exchange 1 day, 120 °C vacuum 6 h; photocatalysis activation: acetonitrile exchange five times in 3 days.
Scalability contextGram scale obtained by combining products from multiple Pyrex tube reactions.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZrCl4(7.4 mg, 0.0318 mmol)S17 · Section 2 Design and synthesis of MOFs · Figure S9
LinkerTML(8.2 mg, 0.00634 mmol)S17 · Section 2 Design and synthesis of MOFs · Figure S9
SolventDEF (1.0 mL)Not specifiedS17 · Section 2 Design and synthesis of MOFs · Figure S9
Additivebenzoic acid(270 mg, 2.214 mmol)S17 · Section 2 Design and synthesis of MOFs · Figure S9
Complete recipeSource: Both

Route 4: Solvothermal

S18 · Section 2 Design and synthesis of MOFs · Figure S10

Metal precursorsZrCl4 (7.4 mg, 0.0318 mmol)
Linker precursorsTM (8.2 mg, 0.00583 mmol)
SolventsDEF (1.0 mL)
Additivesbenzoic acid (270 mg, 2.214 mmol)
Atmospheredegassed by three freeze-pump-thaw cycles; flame sealed under vacuum
Temperature120
Time24
Oxidant / reductantnone for MOF assembly
Work-upyielded dark green cubic crystals; 42% yield based on organic ligand; gram scale obtained by combining products from multiple Pyrex tube reactions
ActivationMain general method: methanol exchange five times in 3 days; porosity activation: DMF wash 3 days, acetone exchange 1 day, 120 °C vacuum 6 h; photocatalysis activation: acetonitrile exchange five times in 3 days.
Scalability contextGram scale obtained by combining products from multiple Pyrex tube reactions.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZrCl4(7.4 mg, 0.0318 mmol)S18 · Section 2 Design and synthesis of MOFs · Figure S10
LinkerTM(8.2 mg, 0.00583 mmol)S18 · Section 2 Design and synthesis of MOFs · Figure S10
SolventDEF (1.0 mL)Not specifiedS18 · Section 2 Design and synthesis of MOFs · Figure S10
Additivebenzoic acid(270 mg, 2.214 mmol)S18 · Section 2 Design and synthesis of MOFs · Figure S10
Complete recipeSource: Both

Route 5: Solvothermal

S19 · Section 2 Design and synthesis of MOFs · Figure S11

Metal precursorsZrCl4 (5.0 mg, 0.0215 mmol)
Linker precursorsTNP (8.5 mg, 0.0057 mmol)
SolventsDEF (1.0 mL)
Additivesbenzoic acid (100 mg, 0.82 mmol)
Atmospheredegassed by three freeze-pump-thaw cycles; flame sealed under vacuum
Temperature120
Time24
Oxidant / reductantnone for MOF assembly
Work-upyielded dark red cubic crystals; 60% yield based on organic ligand; gram scale obtained by combining products from multiple Pyrex tube reactions
ActivationMain general method: methanol exchange five times in 3 days; porosity activation: DMF wash 3 days, acetone exchange 1 day, 120 °C vacuum 6 h; photocatalysis activation: acetonitrile exchange five times in 3 days.
Scalability contextGram scale obtained by combining products from multiple Pyrex tube reactions.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZrCl4(5.0 mg, 0.0215 mmol)S19 · Section 2 Design and synthesis of MOFs · Figure S11
LinkerTNP(8.5 mg, 0.0057 mmol)S19 · Section 2 Design and synthesis of MOFs · Figure S11
SolventDEF (1.0 mL)Not specifiedS19 · Section 2 Design and synthesis of MOFs · Figure S11
Additivebenzoic acid(100 mg, 0.82 mmol)S19 · Section 2 Design and synthesis of MOFs · Figure S11