cMOF Evidence Base

Synthesis evidence

Isoreticular Linker Substitution in Conductive Metal–Organic Frameworks with Through-Space Transport Pathways

Xie L.S., Park S.S., Chmielewski M.J. et al. · Angewandte Chemie - International Edition · 2020 · 19623-19626

13 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

S21 · Synthetic Details

Metal precursorsCd(NO3)2*4H2O (0.0433 g, 0.140 mmol, 4 equiv.)
Linker precursorsH4Ni(dbg)2 (0.0250 g, 0.0351 mmol, 1 equiv.)
Solvents8.0 mL 1:1 H2O/EtOH; 6.0 mL 3:1 DMF/EtOH
Additivesnone
Atmosphereambient/not specified
Temperature75
Time72
Work-upSoaked in 15 mL EtOH for 24 h with 5 solution changes.
ActivationSupercritical CO2 drying; yield 0.0220 g, 67%.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCd(NO3)2*4H2O0.0433 g, 0.140 mmol, 4 equiv.S21 · Synthetic Details
LinkerH4Ni(dbg)20.0250 g, 0.0351 mmol, 1 equiv.S21 · Synthetic Details
Solvent8.0 mL 1:1 H2O/EtOHNot specifiedS21 · Synthetic Details
Solvent6.0 mL 3:1 DMF/EtOHNot specifiedS21 · Synthetic Details
AcidnoneNot specifiedS21 · Synthetic Details
Complete recipeSource: SI

Route 2: Other

S49 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13

Solvents10 mL of 3 mM cobaltocene in MeCN
Additivescobaltocene, 0.03 mmol
Atmospherenitrogen-filled glovebox
Temperature29
Time24
Oxidant / reductantreductant
Work-upCentrifuged/decanted; washed with 2 x 5 mL MeCN; vacuum dried on Schlenk line for 5 h.
Activationsolvent evaporated/removed before conductivity measurement
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Reductantcobaltocene, 0.03 mmolNot specifiedS49 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13
Solvent10 mL of 3 mM cobaltocene in MeCNNot specifiedS49 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13
Complete recipeSource: SI

Route 3: Other

S48 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13

Solvents6 mL of 10 mM I2 in toluene
AdditivesI2, 0.06 mmol
Atmosphereambient/not specified
Temperature100
Time96
Oxidant / reductantoxidant
Work-upCentrifuged/decanted; washed with 3 x 5 mL DCM; solvent evaporated in air.
Activationsolvent evaporated/removed before conductivity measurement
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OxidantI2, 0.06 mmolNot specifiedS48 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13
Solvent6 mL of 10 mM I2 in tolueneNot specifiedS48 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13
Complete recipeSource: SI

Route 4: Other

S48 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13

Solventsiodine vapour in sealed 20 mL vial
AdditivesI2 solid, 0.010 g, 0.040 mmol
Atmosphereambient/not specified
Temperature23
Time32 days
Oxidant / reductantoxidant
Work-upConductivity measured on resulting dull orange powder.
Activationsolvent evaporated/removed before conductivity measurement
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OxidantI2 solid, 0.010 g, 0.040 mmolNot specifiedS48 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13
Solventiodine vapour in sealed 20 mL vialNot specifiedS48 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13
Complete recipeSource: SI

Route 5: Other

S48-S49 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13

Solvents6 mL of 1 mM NOBF4 in MeCN
AdditivesNOBF4, 0.006 mmol
Atmospherenitrogen-filled glovebox
Temperature29
Time24
Oxidant / reductantoxidant
Work-upCentrifuged/decanted; washed with 2 x 5 mL MeCN; vacuum dried on Schlenk line for 5 h.
Activationsolvent evaporated/removed before conductivity measurement
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OxidantNOBF4, 0.006 mmolNot specifiedS48-S49 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13
Solvent6 mL of 1 mM NOBF4 in MeCNNot specifiedS48-S49 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13
Complete recipeSource: SI

Route 6: Solvothermal

S21 · Synthetic Details

Metal precursorsCd(NO3)2*4H2O (0.0087 g, 0.028 mmol, 8.8 equiv.)
Linker precursorsH4Ni(dbg)2 (0.0023 g, 0.0032 mmol, 1 equiv.)
Solvents0.83 mL 1:1 H2O/EtOH; 0.57 mL 3:1 DMF/EtOH
Additives3 uL of 1 M HCl
Atmosphereambient/not specified
Temperature75
Time24
Work-upSoaked in 2 mL EtOH for 24 h with 3 solution changes.
Activationnone reported for diffraction crystals
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCd(NO3)2*4H2O0.0087 g, 0.028 mmol, 8.8 equiv.S21 · Synthetic Details
LinkerH4Ni(dbg)20.0023 g, 0.0032 mmol, 1 equiv.S21 · Synthetic Details
Solvent0.83 mL 1:1 H2O/EtOHNot specifiedS21 · Synthetic Details
Solvent0.57 mL 3:1 DMF/EtOHNot specifiedS21 · Synthetic Details
Acid3 uL of 1 M HClNot specifiedS21 · Synthetic Details
Complete recipeSource: SI

Route 7: Other

S48 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13

Solvents5 mL of 3 mM TCNE in DCM
Additivestetracyanoethylene (TCNE), 0.02 mmol
Atmosphereambient/not specified
Temperature23
Time5 days
Oxidant / reductantoxidant
Work-upCentrifuged/decanted; washed with 3 x 5 mL DCM; solvent evaporated in air.
Activationsolvent evaporated/removed before conductivity measurement
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Oxidanttetracyanoethylene (TCNE), 0.02 mmolNot specifiedS48 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13
Solvent5 mL of 3 mM TCNE in DCMNot specifiedS48 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13
Complete recipeSource: Both

Route 8: Other

S7-S9 · Synthetic Details · Scheme S1

Metal precursorsnickel(II) acetate tetrahydrate (0.249 g, 1.00 mmol) for Na4Ni(dbg)2 formation
Linker precursorsmethyl 4-formylbenzoate -> dimethyl-4,4'-(2-hydroxyacetyl)dibenzoate -> dimethyl-4,4'-oxalyldibenzoate -> 4,4'-oxalyldibenzoic acid -> glyoxime 5 -> Na4Ni(dbg)2 -> H4Ni(dbg)2
SolventsMeOH, water, AcOH, toluene, EtOH, DCM
AdditivesKCN, NH4NO3/copper acetate literature step for 3, H2SO4:H2O 4:1, hydroxylamine, NaOH, AcOH
AtmosphereNitrogen purge and positive nitrogen pressure during Na4Ni(dbg)2 metalation; otherwise not specified.
Temperature30-35; reflux; 60-65; 60 drying
Timemulti-step; includes 15 min benzoin step, overnight reflux steps, 1 h metalation, overnight drying
Work-upFiltration, recrystallisation/sonication, acid wash, DCM wash, centrifugation as described in SI.
ActivationDried under high vacuum at 60 degrees C overnight for H4Ni(dbg)2.
Scalability contextReported isolated yields through linker steps, including 76% for H4Ni(dbg)2.
Show 7 structured reagent records
RoleReagentAmount / concentrationSource
Linkermethyl 4-formylbenzoate8.208 g, 50.00 mmolS7-S9 · Synthetic Details · Scheme S1
Additivepotassium cyanide0.99 g, 15 mmolS7-S9 · Synthetic Details · Scheme S1
Solventmethanol/water35 mL MeOH + 9 mL H2O, then 50 mL H2OS7-S9 · Synthetic Details · Scheme S1
Additivehydroxylamine1.64 mL of 50 wt% aqueous solution, 26.8 mmol · 50 wt%S7-S9 · Synthetic Details · Scheme S1
BaseNaOH60.24 g = 60 mL, 6.00 mmol · 0.100 MS7-S9 · Synthetic Details · Scheme S1
Metal Sourcenickel(II) acetate tetrahydrate0.249 g, 1.00 mmolS7-S9 · Synthetic Details · Scheme S1
Acidanhydrous AcOH15 mL, repeated washesS7-S9 · Synthetic Details · Scheme S1
Complete recipeSource: SI

Route 9: Solvothermal

S20 · Synthetic Details

Metal precursorsMn(NO3)2*4H2O (0.0352 g, 0.140 mmol, 4 equiv.)
Linker precursorsH4Ni(dbg)2 (0.0250 g, 0.0350 mmol, 1 equiv.)
Solvents7.5 mL 1:1 H2O/EtOH; 6.5 mL 3:1 DMF/EtOH
Additivesnone
Atmosphereambient/not specified
Temperature75
Time24
Work-upSoaked in 15 mL EtOH for 24 h with 5 solution changes.
ActivationSupercritical CO2 drying; yield 0.0180 g, 63%.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceMn(NO3)2*4H2O0.0352 g, 0.140 mmol, 4 equiv.S20 · Synthetic Details
LinkerH4Ni(dbg)20.0250 g, 0.0350 mmol, 1 equiv.S20 · Synthetic Details
Solvent7.5 mL 1:1 H2O/EtOHNot specifiedS20 · Synthetic Details
Solvent6.5 mL 3:1 DMF/EtOHNot specifiedS20 · Synthetic Details
AcidnoneNot specifiedS20 · Synthetic Details
Complete recipeSource: SI

Route 10: Other

S48 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13

Solventsiodine vapour in sealed 20 mL vial
AdditivesI2 solid, 0.010 g, 0.040 mmol
Atmosphereambient/not specified
Temperature23
Time32 days
Oxidant / reductantoxidant
Work-upConductivity measured on resulting dull orange powder.
Activationsolvent evaporated/removed before conductivity measurement
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OxidantI2 solid, 0.010 g, 0.040 mmolNot specifiedS48 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13
Solventiodine vapour in sealed 20 mL vialNot specifiedS48 · Attempted doping of MOFs with chemical oxidants and reductants · Table S13
Complete recipeSource: SI

Route 11: Solvothermal

S20 · Synthetic Details

Metal precursorsMn(NO3)2*4H2O (0.0059 g, 0.024 mmol, 6 equiv.)
Linker precursorsH4Ni(dbg)2 (0.0028 g, 0.0040 mmol, 1 equiv.)
Solvents0.70 mL 1:1 H2O/EtOH; 0.70 mL 3:1 DMF/EtOH
Additives4 uL of 1 M HCl
Atmosphereambient/not specified
Temperature75
Time24
Work-upSoaked in 2 mL EtOH for 24 h with 3 solution changes.
Activationnone reported for diffraction crystals
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceMn(NO3)2*4H2O0.0059 g, 0.024 mmol, 6 equiv.S20 · Synthetic Details
LinkerH4Ni(dbg)20.0028 g, 0.0040 mmol, 1 equiv.S20 · Synthetic Details
Solvent0.70 mL 1:1 H2O/EtOHNot specifiedS20 · Synthetic Details
Solvent0.70 mL 3:1 DMF/EtOHNot specifiedS20 · Synthetic Details
Acid4 uL of 1 M HClNot specifiedS20 · Synthetic Details
Complete recipeSource: SI

Route 12: Solvothermal

S20 · Synthetic Details

Metal precursorsZn(NO3)2*6H2O (0.0417 g, 0.140 mmol, 4 equiv.)
Linker precursorsH4Ni(dbg)2 (0.0250 g, 0.0350 mmol, 1 equiv.)
Solvents7.0 mL 1:1 H2O/EtOH; 7.0 mL 3:1 DMF/EtOH
Additivesnone
Atmosphereambient/not specified
Temperature75
Time24
Work-upSoaked in 15 mL EtOH for 24 h with 5 solution changes.
ActivationSupercritical CO2 drying; yield 0.0135 g, 46%.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZn(NO3)2*6H2O0.0417 g, 0.140 mmol, 4 equiv.S20 · Synthetic Details
LinkerH4Ni(dbg)20.0250 g, 0.0350 mmol, 1 equiv.S20 · Synthetic Details
Solvent7.0 mL 1:1 H2O/EtOHNot specifiedS20 · Synthetic Details
Solvent7.0 mL 3:1 DMF/EtOHNot specifiedS20 · Synthetic Details
AcidnoneNot specifiedS20 · Synthetic Details
Complete recipeSource: SI

Route 13: Solvothermal

S20 · Synthetic Details

Metal precursorsZn(NO3)2*6H2O (0.0070 g, 0.024 mmol, 6.9 equiv.)
Linker precursorsH4Ni(dbg)2 (0.0025 g, 0.0035 mmol, 1 equiv.)
Solvents0.70 mL 1:1 H2O/EtOH; 0.70 mL 3:1 DEF/EtOH
Additives4 uL of 1 M HCl
Atmosphereambient/not specified
Temperature75
Time24
Work-upSoaked in 2 mL EtOH for 24 h with 3 solution changes.
Activationnone reported for diffraction crystals
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZn(NO3)2*6H2O0.0070 g, 0.024 mmol, 6.9 equiv.S20 · Synthetic Details
LinkerH4Ni(dbg)20.0025 g, 0.0035 mmol, 1 equiv.S20 · Synthetic Details
Solvent0.70 mL 1:1 H2O/EtOHNot specifiedS20 · Synthetic Details
Solvent0.70 mL 3:1 DEF/EtOHNot specifiedS20 · Synthetic Details
Acid4 uL of 1 M HClNot specifiedS20 · Synthetic Details