cMOF Evidence Base

Synthesis evidence

Effects of Transition Metals on Metal-Octaaminophthalocyanine-Based 2D Metal-Organic Frameworks

Chen G., Li Z., Huang Z. et al. · ACS Nano · 2023 · 9611-9621

10 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Solvothermal

S4 · Methods / Co-CoOAPc synthesis

Metal precursorscobalt(II) nitrate trihydrate Co(NO3)2.6H2O (4.44 mg, 15.3 umol, 3 eq.)
Linker precursorsCoOAPc.8HCl (5 mg, 0.0051 mmol or 5.1 umol, 1 eq.)
Solvents3.5 mL DMF for ligand; metal nitrate in DMF (volume not explicitly stated)
Additives0.75 mL aqueous sodium acetate (NaOAc), 1.6 mol/L
Atmosphereair; loosely capped 20 mL vial
Temperature60
Time4
Oxidant / reductantambient oxygen/air during loosely capped solvothermal reaction; NaOAc as deprotonating agent and coordination modulator
Work-upPreheat ligand solution for 10 min; add NaOAc/metal-nitrate mixture; stir for 4 h; dilute resulting green/black fluid with 20+ mL DI water; vacuum-filter through 0.45 um nylon membrane; wash with DI water, DMF and acetone; dry under vacuum overnight at 60 C
Activationvacuum-dried overnight at 60 C before characterisation
Scalability contextSmall-batch 5 mg linker-scale synthesis; conditions optimised per sample for solvent, base concentration and temperature.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerCoOAPc.8HCl5 mg, 0.0051 mmol or 5.1 umol, 1 eq.S4 · Methods / Co-CoOAPc synthesis
Metal Sourcecobalt(II) nitrate trihydrate Co(NO3)2.6H2O4.44 mg, 15.3 umol, 3 eq.S4 · Methods / Co-CoOAPc synthesis
Basesodium acetate (NaOAc) aqueous0.75 mL · 1.6 mol/LS4 · Methods / Co-CoOAPc synthesis
SolventDMF3.5 mL ligand solvent plus metal-source solventS4 · Methods / Co-CoOAPc synthesis
Complete recipeSource: SI

Route 2: Solvothermal

S3 · Methods / Co-CuOAPc synthesis

Metal precursorscobalt(II) nitrate trihydrate Co(NO3)2.6H2O (4.44 mg, 15.3 umol, 3 eq.)
Linker precursorsCuOAPc.8HCl (5 mg, 0.0051 mmol or 5.1 umol, 1 eq.)
Solvents3.5 mL DMF for ligand; metal nitrate in DMF
Additives0.75 mL aqueous sodium acetate (NaOAc), 1.6 mol/L
Atmosphereair; loosely capped 20 mL vial
Temperature60
Time4
Oxidant / reductantambient oxygen/air during loosely capped solvothermal reaction; NaOAc as deprotonating agent and coordination modulator
Work-upPreheat ligand solution for 10 min; add NaOAc/metal-nitrate mixture; stir for 4 h; dilute resulting green/black fluid with 20+ mL DI water; vacuum-filter through 0.45 um nylon membrane; wash with DI water, DMF and acetone; dry under vacuum overnight at 60 C
Activationvacuum-dried overnight at 60 C before characterisation
Scalability contextSmall-batch 5 mg linker-scale synthesis; conditions optimised per sample for solvent, base concentration and temperature.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerCuOAPc.8HCl5 mg, 0.0051 mmol or 5.1 umol, 1 eq.S3 · Methods / Co-CuOAPc synthesis
Metal Sourcecobalt(II) nitrate trihydrate Co(NO3)2.6H2O4.44 mg, 15.3 umol, 3 eq.S3 · Methods / Co-CuOAPc synthesis
Basesodium acetate (NaOAc) aqueous0.75 mL · 1.6 mol/LS3 · Methods / Co-CuOAPc synthesis
SolventDMF3.5 mL ligand solvent plus metal-source solventS3 · Methods / Co-CuOAPc synthesis
Complete recipeSource: SI

Route 3: Solvothermal

S3 · Methods / Co-NiOAPc synthesis

Metal precursorscobalt(II) nitrate trihydrate Co(NO3)2.6H2O (4.44 mg, 15.3 umol, 3 eq.)
Linker precursorsNiOAPc.8HCl (5 mg, 0.0051 mmol or 5.1 umol, 1 eq.)
Solvents3.5 mL DMF for ligand; metal nitrate in DMF
Additives0.75 mL aqueous sodium acetate (NaOAc), 1.6 mol/L
Atmosphereair; loosely capped 20 mL vial
Temperature60
Time4
Oxidant / reductantambient oxygen/air during loosely capped solvothermal reaction; NaOAc as deprotonating agent and coordination modulator
Work-upPreheat ligand solution for 10 min; add NaOAc/metal-nitrate mixture; stir for 4 h; dilute resulting green/black fluid with 20+ mL DI water; vacuum-filter through 0.45 um nylon membrane; wash with DI water, DMF and acetone; dry under vacuum overnight at 60 C
Activationvacuum-dried overnight at 60 C before characterisation
Scalability contextSmall-batch 5 mg linker-scale synthesis; conditions optimised per sample for solvent, base concentration and temperature.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerNiOAPc.8HCl5 mg, 0.0051 mmol or 5.1 umol, 1 eq.S3 · Methods / Co-NiOAPc synthesis
Metal Sourcecobalt(II) nitrate trihydrate Co(NO3)2.6H2O4.44 mg, 15.3 umol, 3 eq.S3 · Methods / Co-NiOAPc synthesis
Basesodium acetate (NaOAc) aqueous0.75 mL · 1.6 mol/LS3 · Methods / Co-NiOAPc synthesis
SolventDMF3.5 mL ligand solvent plus metal-source solventS3 · Methods / Co-NiOAPc synthesis
Complete recipeSource: SI

Route 4: Solvothermal

S2 · Methods / Cu-CoOAPc synthesis

Metal precursorscopper(II) nitrate trihydrate Cu(NO3)2.3H2O (3.68 mg, 15.2 umol, 3 eq.)
Linker precursorsCoOAPc.8HCl (5 mg, 0.0051 mmol or 5.1 umol, 1 eq.)
Solvents3.5 mL DMF for ligand + 1.5 mL DMF for nitrate
Additives0.75 mL aqueous sodium acetate (NaOAc), 3.2 mol/L
Atmosphereair; loosely capped 20 mL vial
Temperature60
Time4
Oxidant / reductantambient oxygen/air during loosely capped solvothermal reaction; NaOAc as deprotonating agent and coordination modulator
Work-upPreheat ligand solution for 10 min; add NaOAc/metal-nitrate mixture; stir for 4 h; dilute resulting green/black fluid with 20+ mL DI water; vacuum-filter through 0.45 um nylon membrane; wash with DI water, DMF and acetone; dry under vacuum overnight at 60 C
Activationvacuum-dried overnight at 60 C before characterisation
Scalability contextSmall-batch 5 mg linker-scale synthesis; conditions optimised per sample for solvent, base concentration and temperature.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerCoOAPc.8HCl5 mg, 0.0051 mmol or 5.1 umol, 1 eq.S2 · Methods / Cu-CoOAPc synthesis
Metal Sourcecopper(II) nitrate trihydrate Cu(NO3)2.3H2O3.68 mg, 15.2 umol, 3 eq.S2 · Methods / Cu-CoOAPc synthesis
Basesodium acetate (NaOAc) aqueous0.75 mL · 3.2 mol/LS2 · Methods / Cu-CoOAPc synthesis
SolventDMF3.5 mL ligand solvent plus metal-source solventS2 · Methods / Cu-CoOAPc synthesis
Complete recipeSource: Both

Route 5: Solvothermal

S2 · Methods / Cu-CuOAPc synthesis

Metal precursorscopper(II) nitrate trihydrate Cu(NO3)2.3H2O (3.68 mg, 15.2 umol, 3 eq.)
Linker precursorsCuOAPc.8HCl (5 mg, 0.0051 mmol or 5.1 umol, 1 eq.)
Solvents3.5 mL DMA for ligand + 1.5 mL DMA for nitrate
Additives0.75 mL aqueous sodium acetate (NaOAc), 1.6 mol/L
Atmosphereair; loosely capped 20 mL vial
Temperature70
Time4
Oxidant / reductantambient oxygen/air during loosely capped solvothermal reaction; NaOAc as deprotonating agent and coordination modulator
Work-upPreheat ligand solution for 10 min; add NaOAc/metal-nitrate mixture; stir for 4 h; dilute resulting green/black fluid with 20+ mL DI water; vacuum-filter through 0.45 um nylon membrane; wash with DI water, DMF and acetone; dry under vacuum overnight at 60 C
Activationvacuum-dried overnight at 60 C before characterisation
Scalability contextSmall-batch 5 mg linker-scale synthesis; conditions optimised per sample for solvent, base concentration and temperature.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerCuOAPc.8HCl5 mg, 0.0051 mmol or 5.1 umol, 1 eq.S2 · Methods / Cu-CuOAPc synthesis
Metal Sourcecopper(II) nitrate trihydrate Cu(NO3)2.3H2O3.68 mg, 15.2 umol, 3 eq.S2 · Methods / Cu-CuOAPc synthesis
Basesodium acetate (NaOAc) aqueous0.75 mL · 1.6 mol/LS2 · Methods / Cu-CuOAPc synthesis
SolventDMA3.5 mL ligand solvent plus metal-source solventS2 · Methods / Cu-CuOAPc synthesis
Complete recipeSource: SI

Route 6: Solvothermal

S2 · Methods / Cu-NiOAPc synthesis

Metal precursorscopper(II) nitrate trihydrate Cu(NO3)2.3H2O (3.68 mg, 15.2 umol, 3 eq.)
Linker precursorsNiOAPc.8HCl (5 mg, 0.0051 mmol or 5.1 umol, 1 eq.)
Solvents3.5 mL DMA for ligand + 1.5 mL DMA for nitrate
Additives0.75 mL aqueous sodium acetate (NaOAc), 1.6 mol/L
Atmosphereair; loosely capped 20 mL vial
Temperature70
Time4
Oxidant / reductantambient oxygen/air during loosely capped solvothermal reaction; NaOAc as deprotonating agent and coordination modulator
Work-upPreheat ligand solution for 10 min; add NaOAc/metal-nitrate mixture; stir for 4 h; dilute resulting green/black fluid with 20+ mL DI water; vacuum-filter through 0.45 um nylon membrane; wash with DI water, DMF and acetone; dry under vacuum overnight at 60 C
Activationvacuum-dried overnight at 60 C before characterisation
Scalability contextSmall-batch 5 mg linker-scale synthesis; conditions optimised per sample for solvent, base concentration and temperature.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerNiOAPc.8HCl5 mg, 0.0051 mmol or 5.1 umol, 1 eq.S2 · Methods / Cu-NiOAPc synthesis
Metal Sourcecopper(II) nitrate trihydrate Cu(NO3)2.3H2O3.68 mg, 15.2 umol, 3 eq.S2 · Methods / Cu-NiOAPc synthesis
Basesodium acetate (NaOAc) aqueous0.75 mL · 1.6 mol/LS2 · Methods / Cu-NiOAPc synthesis
SolventDMA3.5 mL ligand solvent plus metal-source solventS2 · Methods / Cu-NiOAPc synthesis
Complete recipeSource: Main

Route 7: Other

9619 · Methods / Syntheses of Metal(II) octaaminophthalocyanine ligand

Metal precursorscopper(II) acetate; CoOAPc and NiOAPc prepared analogously with cobalt(II) acetate / nickel(II) acetate tetrahydrate
Linker precursors4,5-bis((diphenylmethylene)amino)phthalonitrile
Solventsmolecular-sieve dried n-pentanol; THF for HCl hydrolysis
AdditivesDBU; aqueous HCl
Atmospherenitrogen during cyclotetramerisation and hydrolysis
Temperature155 then 45
Time48 then 0.5
Work-upfiltered and washed with methanol/ethanol; acetone sonication/washing until filtrate nearly colourless; dissolved in dichloromethane or chloroform and filtered; HCl hydrolysis, filtered, N2-bubbled acetone wash, vacuum drying
Activationvacuum dried
Scalability contextPublished procedure with slight modifications; authors emphasise acetone washing of precursor for ligand purity.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Linker4,5-bis((diphenylmethylene)amino)phthalonitrile1 g, 2.06 mmol9619 · Methods / Syntheses of Metal(II) octaaminophthalocyanine ligand
Metal Sourcecopper(II) acetate (or cobalt/nickel acetate for CoOAPc/NiOAPc)124.12 mg, 683 mmol as written for copper acetate9619 · Methods / Syntheses of Metal(II) octaaminophthalocyanine ligand
BaseDBU391.10 mg, 2.57 mmol9619 · Methods / Syntheses of Metal(II) octaaminophthalocyanine ligand
Solventn-pentanol120 mL9619 · Methods / Syntheses of Metal(II) octaaminophthalocyanine ligand
Acidaqueous HCl6 mL, 12 mmol · 2.0 M9619 · Methods / Syntheses of Metal(II) octaaminophthalocyanine ligand
Complete recipeSource: SI

Route 8: Solvothermal

S3-S4 · Methods / Ni-CoOAPc synthesis

Metal precursorsnickel(II) nitrate hexahydrate Ni(NO3)2.6H2O (4.43 mg, 15.2 umol, 3 eq.)
Linker precursorsCoOAPc.8HCl (5 mg, 0.0051 mmol or 5.1 umol, 1 eq.)
Solvents3.5 mL DMF for ligand; metal nitrate solvent volume not clearly stated
Additives0.75 mL aqueous sodium acetate (NaOAc), 1.6 mol/L
Atmosphereair; loosely capped 20 mL vial
Temperature60
Time4
Oxidant / reductantambient oxygen/air during loosely capped solvothermal reaction; NaOAc as deprotonating agent and coordination modulator
Work-upPreheat ligand solution for 10 min; add NaOAc/metal-nitrate mixture; stir for 4 h; dilute resulting green/black fluid with 20+ mL DI water; vacuum-filter through 0.45 um nylon membrane; wash with DI water, DMF and acetone; dry under vacuum overnight at 60 C
Activationvacuum-dried overnight at 60 C before characterisation
Scalability contextSmall-batch 5 mg linker-scale synthesis; conditions optimised per sample for solvent, base concentration and temperature.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerCoOAPc.8HCl5 mg, 0.0051 mmol or 5.1 umol, 1 eq.S3-S4 · Methods / Ni-CoOAPc synthesis
Metal Sourcenickel(II) nitrate hexahydrate Ni(NO3)2.6H2O4.43 mg, 15.2 umol, 3 eq.S3-S4 · Methods / Ni-CoOAPc synthesis
Basesodium acetate (NaOAc) aqueous0.75 mL · 1.6 mol/LS3-S4 · Methods / Ni-CoOAPc synthesis
SolventDMF3.5 mL ligand solvent plus metal-source solventS3-S4 · Methods / Ni-CoOAPc synthesis
Complete recipeSource: SI

Route 9: Solvothermal

S3 · Methods / Ni-CuOAPc synthesis

Metal precursorsnickel(II) nitrate hexahydrate Ni(NO3)2.6H2O (4.43 mg, 15.2 umol, 3 eq.)
Linker precursorsCuOAPc.8HCl (5 mg, 0.0051 mmol or 5.1 umol, 1 eq.)
Solvents3.5 mL DMF for ligand + 1.5 mL DMF for nitrate
Additives0.75 mL aqueous sodium acetate (NaOAc), 1.6 mol/L
Atmosphereair; loosely capped 20 mL vial
Temperature70
Time4
Oxidant / reductantambient oxygen/air during loosely capped solvothermal reaction; NaOAc as deprotonating agent and coordination modulator
Work-upPreheat ligand solution for 10 min; add NaOAc/metal-nitrate mixture; stir for 4 h; dilute resulting green/black fluid with 20+ mL DI water; vacuum-filter through 0.45 um nylon membrane; wash with DI water, DMF and acetone; dry under vacuum overnight at 60 C
Activationvacuum-dried overnight at 60 C before characterisation
Scalability contextSmall-batch 5 mg linker-scale synthesis; conditions optimised per sample for solvent, base concentration and temperature.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerCuOAPc.8HCl5 mg, 0.0051 mmol or 5.1 umol, 1 eq.S3 · Methods / Ni-CuOAPc synthesis
Metal Sourcenickel(II) nitrate hexahydrate Ni(NO3)2.6H2O4.43 mg, 15.2 umol, 3 eq.S3 · Methods / Ni-CuOAPc synthesis
Basesodium acetate (NaOAc) aqueous0.75 mL · 1.6 mol/LS3 · Methods / Ni-CuOAPc synthesis
SolventDMF3.5 mL ligand solvent plus metal-source solventS3 · Methods / Ni-CuOAPc synthesis
Complete recipeSource: SI

Route 10: Solvothermal

S3 · Methods / Ni-NiOAPc synthesis

Metal precursorsnickel(II) nitrate hexahydrate Ni(NO3)2.6H2O (4.43 mg, 15.2 umol, 3 eq.)
Linker precursorsNiOAPc.8HCl (5 mg, 0.0051 mmol or 5.1 umol, 1 eq.)
Solvents3.5 mL DMF for ligand + 1.5 mL DMF for nitrate
Additives0.75 mL aqueous sodium acetate (NaOAc), 1.6 mol/L
Atmosphereair; loosely capped 20 mL vial
Temperature70
Time4
Oxidant / reductantambient oxygen/air during loosely capped solvothermal reaction; NaOAc as deprotonating agent and coordination modulator
Work-upPreheat ligand solution for 10 min; add NaOAc/metal-nitrate mixture; stir for 4 h; dilute resulting green/black fluid with 20+ mL DI water; vacuum-filter through 0.45 um nylon membrane; wash with DI water, DMF and acetone; dry under vacuum overnight at 60 C
Activationvacuum-dried overnight at 60 C before characterisation
Scalability contextSmall-batch 5 mg linker-scale synthesis; conditions optimised per sample for solvent, base concentration and temperature.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerNiOAPc.8HCl5 mg, 0.0051 mmol or 5.1 umol, 1 eq.S3 · Methods / Ni-NiOAPc synthesis
Metal Sourcenickel(II) nitrate hexahydrate Ni(NO3)2.6H2O4.43 mg, 15.2 umol, 3 eq.S3 · Methods / Ni-NiOAPc synthesis
Basesodium acetate (NaOAc) aqueous0.75 mL · 1.6 mol/LS3 · Methods / Ni-NiOAPc synthesis
SolventDMF3.5 mL ligand solvent plus metal-source solventS3 · Methods / Ni-NiOAPc synthesis