Synthesis evidence

Effects of intervalence charge transfer interaction between π-stacked mixed valent tetrathiafulvalene ligands on the electrical conductivity of 3D metal-organic frameworks

Zhang S., Panda D.K., Yadav A. et al. · Chemical Science · 2021 · 13379-13391

6 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Other

S4-S5 · Material Synthesis and Characterization

Metal precursors0.5 M CsOH solution (0.15 mL)
Linker precursorsTTFTC-Me4 (5 mg, 0.0115 mmol), converted by in situ saponification
Solvents1:2 THF/MeOH mixture (1.5 mL) in inner vial; 1:1 THF/MeOH (5 mL) in outer vial for vapour diffusion
AdditivesCsOH base
Atmosphereambient in screw-capped vial
Temperature20
Time72
Oxidant / reductantnone; material remained unchanged on air exposure
Work-upfiltered, rinsed with MeCN three times, soaked in MeCN for 12 h
Activationfiltered and dried under vacuum for 24 h
Scalability context5 mL inner vial/20 mL outer vial vapour-diffusion crystal synthesis; yield 10.91 mg (84%).
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
LinkerTTFTC-Me45 mg, 0.0115 mmolS4-S5 · Material Synthesis and Characterization
BaseCsOH solution0.15 mL · 0.5 MS4-S5 · Material Synthesis and Characterization
SolventTHF/MeOH inner solution1.5 mL · 1:2 mixtureS4-S5 · Material Synthesis and Characterization
SolventTHF/MeOH outer vapour reservoir5 mL · 1:1 mixtureS4-S5 · Material Synthesis and Characterization
SolventMeCNrinse three times; soak 12 hS4-S5 · Material Synthesis and Characterization
Complete recipeSource: Both

Route 2: Solvothermal

S4 · Material Synthesis and Characterization

Metal precursors0.5 M KOH solution (0.6 mL)
Linker precursorsTTFTC-Me4 (20 mg, 0.046 mmol), converted by in situ saponification
Solvents1:2 THF/MeOH mixture (6 mL); aqueous KOH contributes H2O
AdditivesKOH base
Atmosphereambient/air
Temperature80
Time2
Oxidant / reductantnone intentional for fresh 2; partial aerobic TTFTC•+ population present
Work-upfiltered, rinsed with CH3CN three times, soaked in MeCN for 12 h
Activationfiltered and dried under vacuum for 24 h
Scalability context20 mL vial small-batch crystal synthesis; yield 21.35 mg (77%).
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerTTFTC-Me420 mg, 0.046 mmolS4 · Material Synthesis and Characterization
BaseKOH solution0.6 mL · 0.5 MS4 · Material Synthesis and Characterization
SolventTHF/MeOH6 mL · 1:2 mixtureS4 · Material Synthesis and Characterization
SolventCH3CN/MeCNrinse three times; soak 12 hS4 · Material Synthesis and Characterization
Complete recipeSource: Both

Route 3: Other

S4 · Material Synthesis and Characterization

Metal precursorsK-MOF 2
Linker precursorsTTFTC ligands within K-MOF 2
Solventsnone
Additivesnone
Atmosphereair
Temperatureambient
Time168
Oxidant / reductantO2/air aerobic oxidation of TTFTC to TTFTC•+
Work-upexposed to air for 7 d until dark brown/black crystalline powder
Activationnone additional reported
Scalability contextpost-synthetic air oxidation of bulk powder
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OtherK-MOF 2not separately specifiedS4 · Material Synthesis and Characterization
Oxidantair/O27 d exposureS4 · Material Synthesis and Characterization
Complete recipeSource: Both

Route 4: Solvothermal

S4 · Material Synthesis and Characterization

Metal precursors0.5 M NaOH solution (1.6 mL)
Linker precursorsTTFTC-Me4 (20 mg, 0.046 mmol), converted by in situ saponification
Solvents1:2 THF/MeOH mixture (6 mL); aqueous NaOH contributes H2O
AdditivesNaOH base
Atmosphereair/ambient; aerobic oxidation implicit in product 1-ox
Temperature65
Time12
Oxidant / reductantaerobic oxidation to TTFTC•+ radical cations during/after synthesis
Work-upfiltered, rinsed thoroughly with MeCN three times, soaked in MeCN for 12 h
Activationfiltered and dried under vacuum for 24 h
Scalability context20 mL vial small-batch crystal synthesis; yield 21.40 mg (91%).
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerTTFTC-Me420 mg, 0.046 mmolS4 · Material Synthesis and Characterization
BaseNaOH solution1.6 mL · 0.5 MS4 · Material Synthesis and Characterization
SolventTHF/MeOH6 mL · 1:2 mixtureS4 · Material Synthesis and Characterization
SolventMeCNrinse three times; soak 12 hS4 · Material Synthesis and Characterization
Complete recipeSource: Both

Route 5: Solvothermal

S4 · Material Synthesis and Characterization

Metal precursors0.5 M RbOH solution (0.6 mL)
Linker precursorsTTFTC-Me4 (20 mg, 0.046 mmol), converted by in situ saponification
Solvents1:2 THF/MeOH mixture (6 mL); aqueous RbOH contributes H2O
AdditivesRbOH base
Atmosphereambient/air
Temperature65
Time12
Oxidant / reductantnone intentional for fresh 3; negligible initial TTFTC•+ population
Work-upfiltered, rinsed with MeCN three times, soaked in MeCN for 12 h
Activationfiltered and dried under vacuum for 24 h
Scalability context20 mL vial small-batch crystal synthesis; yield 27.25 mg (75%).
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
LinkerTTFTC-Me420 mg, 0.046 mmolS4 · Material Synthesis and Characterization
BaseRbOH solution0.6 mL · 0.5 MS4 · Material Synthesis and Characterization
SolventTHF/MeOH6 mL · 1:2 mixtureS4 · Material Synthesis and Characterization
SolventMeCNrinse three times; soak 12 hS4 · Material Synthesis and Characterization
Complete recipeSource: Both

Route 6: Other

S4 · Material Synthesis and Characterization

Metal precursorsRb-MOF 3
Linker precursorsTTFTC ligands within Rb-MOF 3
Solventsnone
Additivesnone
Atmosphereair
Temperatureambient
Time168
Oxidant / reductantO2/air aerobic oxidation of TTFTC to TTFTC•+
Work-upexposed to air for 7 d until black crystalline powder
Activationnone additional reported
Scalability contextpost-synthetic air oxidation of bulk powder
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
OtherRb-MOF 3not separately specifiedS4 · Material Synthesis and Characterization
Oxidantair/O27 d exposureS4 · Material Synthesis and Characterization