cMOF Evidence Base

Synthesis evidence

A Novel Electrically Conductive Perylene Diimide-Based MOF-74 Series Featuring Luminescence and Redox Activity

Scheurle P.I., Biewald A., Mahringer A. et al. · Small Structures · 2022 · 2100195

5 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Other

7 · Synthetic procedures · Scheme 1

Metal precursorsZn(OAc)2 used as additive/catalyst, not framework metal
Linker precursorsperylene-3,4,9,10-tetracarboxylic dianhydride; 5-amino-2-hydroxy benzoic acid
Solventsimidazole melt; acid/water/methanol workup
Additivesimidazole; Zn(OAc)2; 2 M hydrochloric acid workup
Atmospherenitrogen atmosphere during heating
Temperature100 C for 2 h, then 140 C for 20 h
Time22
Work-upcooled; 100 mL 2 M HCl added; filtered; washed with 2 M HCl (600 mL), hot water (800 mL), methanol (50 mL)
Activationdried under reduced pressure
Scalability context500 mg dianhydride scale; 545 mg product, 65% yield.
Show 7 structured reagent records
RoleReagentAmount / concentrationSource
Linkerperylene-3,4,9,10-tetracarboxylic dianhydride500 mg, 1.27 mmol, 1 eq7 · Synthetic procedures · Scheme 1
Linker5-amino-2-hydroxy benzoic acid487 mg, 3.18 mmol, 2.5 eq7 · Synthetic procedures · Scheme 1
Baseimidazole20 g, 293.8 mmol, 231 eq7 · Synthetic procedures · Scheme 1
AdditiveZn(OAc)2100 mg, 0.456 mmol, 0.36 eq7 · Synthetic procedures · Scheme 1
Acidhydrochloric acid100 mL added; 600 mL wash · 2 M7 · Synthetic procedures · Scheme 1
Solventhot water800 mL wash7 · Synthetic procedures · Scheme 1
Solventmethanol50 mL wash7 · Synthetic procedures · Scheme 1
Complete recipeSource: Both

Route 2: Solvothermal

8 · PDI-MOF-74(Mg)

Metal precursorsMg(NO3)2.6H2O
Linker precursorsPDI-based ligand
SolventsDMF; MeOH
Additivesacetic acid
Atmospherehandled in air unless otherwise noted; sealed Schott Duran vial atmosphere not specified
Temperature120
Time48
Work-upsonicated 1 h; heated in 25 mL Schott Duran vial; precipitate washed with DMF (4 x 30 mL), soaked in MeOH (1 x 30 mL, 1 h) and THF (1 x 30 mL, 1 h), filtered
Activationevacuated at 120 C to remove less volatile solvents; sorption samples activated under high vacuum at 120 C for at least 12 h
Scalability context0.02 mmol linker scale; dark red crystalline powder obtained.
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
LinkerPDI-based ligand12.9 mg, 0.02 mmol, 1 eq8 · PDI-MOF-74(Mg)
Metal SourceMg(NO3)2.6H2O21.68 mg, 0.08 mmol, 4 eq8 · PDI-MOF-74(Mg)
SolventDMF10 mL8 · PDI-MOF-74(Mg)
SolventMeOH4 mL plus 1 x 30 mL soak, 1 h8 · PDI-MOF-74(Mg)
Acidacetic acid10 uL, 0.17 mmol, 8.7 eq8 · PDI-MOF-74(Mg)
SolventTHF1 x 30 mL soak, 1 h8 · PDI-MOF-74(Mg)
Complete recipeSource: Both

Route 3: Solvothermal

8-9 · PDI-MOF-74(Ni)

Metal precursorsNiCl2.6H2O
Linker precursorsPDI-based ligand
SolventsDMF; BnOH
Additivesnone reported
Atmospherehandled in air unless otherwise noted; culture tube atmosphere not specified
Temperature120
Time48
Work-upsonicated 1 h; heated in culture tube; precipitate washed with DMF (4 x 30 mL), soaked in MeOH (1 x 30 mL, 1 h) and THF (1 x 30 mL, 1 h), filtered
Activationevacuated at 120 C to remove less volatile solvents; sorption samples activated under high vacuum at 120 C for at least 12 h
Scalability context0.016 mmol linker scale; dark red crystalline powder obtained.
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
LinkerPDI-based ligand10.37 mg, 0.016 mmol, 1 eq8-9 · PDI-MOF-74(Ni)
Metal SourceNiCl2.6H2O14.30 mg, 0.07 mmol, 4.4 eq8-9 · PDI-MOF-74(Ni)
SolventDMF2 mL8-9 · PDI-MOF-74(Ni)
SolventBnOH2 mL8-9 · PDI-MOF-74(Ni)
SolventMeOH1 x 30 mL soak, 1 h8-9 · PDI-MOF-74(Ni)
SolventTHF1 x 30 mL soak, 1 h8-9 · PDI-MOF-74(Ni)
Complete recipeSource: Both

Route 4: Drop Cast

6, 9 · Film formation via vapor-assisted conversion (VAC) · Figure S30

Metal precursorsZn(NO3)2.6H2O
Linker precursorsPDI-based ligand
SolventsDMF vapour; DMF precursor solution
Additivessalicylic acid modulator
Atmosphereclosed glass bottle; substrate dried in nitrogen flow before use
Temperature120
Time48
Substrate orientationglass substrate on elevated Raschig-ring platform in DMF-containing bottle
Work-upglass substrate removed after cooling and dried under reduced pressure
Activationdried under reduced pressure
Scalability context100 uL precursor droplet on 1.2 cm x 1.0 cm glass substrate; film thickness around 17 um.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerPDI-based ligand3.17 mg, 4.9 mmol, 1 eq.6, 9 · Film formation via vapor-assisted conversion (VAC) · Figure S30
SolventDMF1.1 mL precursor solution; 5 mL in VAC bottle6, 9 · Film formation via vapor-assisted conversion (VAC) · Figure S30
Additivesalicylic acid25 uL from a solution of 424 mg salicylic acid in 2 mL DMF6, 9 · Film formation via vapor-assisted conversion (VAC) · Figure S30
Metal SourceZn(NO3)2.6H2O2.60 mg, 9.8 mmol, 2 eq6, 9 · Film formation via vapor-assisted conversion (VAC) · Figure S30
Complete recipeSource: Both

Route 5: Solvothermal

8 · PDI-MOF-74(Zn)

Metal precursorsZn(NO3)2.4H2O
Linker precursorsPDI-based ligand
SolventsDMF
Additivesacetic acid
Atmospherehandled in air unless otherwise noted; sealed Schott Duran vial atmosphere not specified
Temperature120
Time48
Work-upsonicated 1 h; heated in 50 mL Schott Duran vial; precipitate washed with DMF (4 x 30 mL), soaked in MeOH (1 x 30 mL, 1 h) and THF (1 x 30 mL, 1 h), filtered
Activationevacuated at 120 C to remove less volatile solvents; sorption samples activated under high vacuum at 120 C for at least 12 h
Scalability context0.06 mmol linker scale; dark red crystalline powder obtained.
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
LinkerPDI-based ligand38.7 mg, 0.06 mmol, 1 eq8 · PDI-MOF-74(Zn)
Metal SourceZn(NO3)2.4H2O58.17 mg, 0.22 mmol, 3.7 eq8 · PDI-MOF-74(Zn)
SolventDMF18 mL8 · PDI-MOF-74(Zn)
Acidacetic acid12 uL, 0.21 mmol, 10.5 eq8 · PDI-MOF-74(Zn)
SolventMeOH1 x 30 mL soak, 1 h8 · PDI-MOF-74(Zn)
SolventTHF1 x 30 mL soak, 1 h8 · PDI-MOF-74(Zn)