Synthesis evidence

Electrochromism in Isoreticular Metal-Organic Framework Thin Films with Record High Coloration Efficiency

Kumar A., Li J., Inge A.K. et al. · ACS Nano · 2023 · 21595-21603

9 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

4-5 · Synthesis and characterization of linkers

Metal precursorsnone
Linker precursors1,4,5,8 naphthalene tetracarboxylic dianhydride (0.86 g, 3.2 mmol); 4-amino-3,5-dimethylpyrazole (0.75 g, 6.8 mmol)
Solventsanhydrous DMF (50 mL)
Additivesnone stated
Atmosphereargon
Temperature140
Time12
Substrate orientationnot applicable
Oxidant / reductantnone stated
Work-upcooled; dark brown DMF solution poured into diethyl ether (150 mL); precipitate collected by filtration; recrystallized from DMF/diethyl ether (10 mL:20 mL); dried in vacuo at 70 C
Activationdried under vacuum/in vacuo as stated
Scalability contextSchlenk flask scale; no scale-up study reported
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Linker1,4,5,8 naphthalene tetracarboxylic dianhydride0.86 g, 3.2 mmol4-5 · Synthesis and characterization of linkers
Linker4-amino-3,5-dimethylpyrazole0.75 g, 6.8 mmol4-5 · Synthesis and characterization of linkers
Solventanhydrous DMF50 mL4-5 · Synthesis and characterization of linkers
Complete recipeSource: SI

Route 2: Other

4-5 · Synthesis and characterization of linkers

Metal precursorsnone
Linker precursors1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride (0.996 g, 1.88 mmol); 4-amino-3,5-dimethylpyrazole (1.048 g, 9.44 mmol)
Solventspropionic acid (20 mL)
Additivespropionic acid acts as solvent/reaction medium
Atmosphereargon
Temperature140
Time24
Substrate orientationnot applicable
Oxidant / reductantnone stated
Work-upcooled; precipitate filtered and washed with deionized water until neutral; crude product extracted with dichloromethane; dried in vacuo
Activationdried under vacuum/in vacuo as stated
Scalability contextSchlenk flask scale; no scale-up study reported
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Linker1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride0.996 g, 1.88 mmol4-5 · Synthesis and characterization of linkers
Linker4-amino-3,5-dimethylpyrazole1.048 g, 9.44 mmol4-5 · Synthesis and characterization of linkers
Solventpropionic acid20 mL4-5 · Synthesis and characterization of linkers
Complete recipeSource: SI

Route 3: Other

4-5 · Synthesis and characterization of linkers

Metal precursorsnone
Linker precursorspyromellitic dianhydride (0.5 g, 2.29 mmol); 4-amino-3,5-dimethylpyrazole (1.1 g, 5 mmol)
Solventsanhydrous N,N-dimethylacetamide (25 mL)
Additivesnone stated
Atmosphereargon
Temperature130
Time8
Substrate orientationnot applicable
Oxidant / reductantnone stated
Work-upfiltered and washed with successive aliquots of dichloromethane; dried under vacuum; recrystallized from DCM
Activationdried under vacuum/in vacuo as stated
Scalability contextSchlenk flask scale; no scale-up study reported
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Linkerpyromellitic dianhydride0.5 g, 2.29 mmol4-5 · Synthesis and characterization of linkers
Linker4-amino-3,5-dimethylpyrazole1.1 g, 5 mmol4-5 · Synthesis and characterization of linkers
Solventanhydrous N,N-dimethylacetamide25 mL4-5 · Synthesis and characterization of linkers
Complete recipeSource: Both

Route 4: Solvothermal

9 · Thin film formation

Metal precursorsZn(NO3)2.6H2O (0.11 mmol)
Linker precursorsNDI (0.10 mmol)
SolventsDMF
AdditivesAlconox, ethanol and acetone used for FTO cleaning; KPF6 only for later electrochemistry, not synthesis
Atmospheredeaerated by bubbling argon for 10 min before sealing
Temperature130
Time4.5
Substrate orientationprecleaned FTO slides inserted with FTO side facing down
Oxidant / reductantnone stated
Work-upcooled to room temperature; films washed with DMF and sonicated 1 min to remove loosely bound powder
Activationsoaked in DMF until further use; no thermal/vacuum activation reported for films
Scalability contextFTO pieces were 2.5 x 1.1 cm2 in a 20 mL scintillation vial; no scale-up study reported
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZn (NO3)2.6H2O0.11 mmol9 · Thin film formation
LinkerNDI0.10 mmol9 · Thin film formation
SolventDMFnot stated9 · Thin film formation
AdditiveAlconox (1%)used for FTO cleaning · 1%9 · Thin film formation
Solventethanolused for FTO cleaning9 · Thin film formation
Solventacetoneused for FTO cleaning9 · Thin film formation
Partial recipeSource: Main

Route 5: Solvothermal

7 · General Methods

Metal precursorsZn(NO3)2.6H2O; 1.1 equiv relative to XDI
Linker precursorsNDI; 1 equiv
SolventsDMF
Additivesnone stated
Atmospherenot stated for powder route
Temperature130
Time4
Substrate orientationnot applicable
Oxidant / reductantnone stated
Work-upnot stated
Activationnot stated
Scalability contextBulk powder route reported only in summary form.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZn (NO3)2.6H2O1.1 molar equivalents7 · General Methods
LinkerNDI1 molar equivalent7 · General Methods
SolventDMFnot stated7 · General Methods
Complete recipeSource: Both

Route 6: Solvothermal

9 · Thin film formation

Metal precursorsZn(NO3)2.6H2O (0.11 mmol)
Linker precursorsPDI (0.10 mmol)
SolventsDMF
AdditivesAlconox, ethanol and acetone used for FTO cleaning; KPF6 only for later electrochemistry, not synthesis
Atmospheredeaerated by bubbling argon for 10 min before sealing
Temperature130
Time4.5
Substrate orientationprecleaned FTO slides inserted with FTO side facing down
Oxidant / reductantnone stated
Work-upcooled to room temperature; films washed with DMF and sonicated 1 min to remove loosely bound powder
Activationsoaked in DMF until further use; no thermal/vacuum activation reported for films
Scalability contextFTO pieces were 2.5 x 1.1 cm2 in a 20 mL scintillation vial; no scale-up study reported
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZn (NO3)2.6H2O0.11 mmol9 · Thin film formation
LinkerPDI0.10 mmol9 · Thin film formation
SolventDMFnot stated9 · Thin film formation
AdditiveAlconox (1%)used for FTO cleaning · 1%9 · Thin film formation
Solventethanolused for FTO cleaning9 · Thin film formation
Solventacetoneused for FTO cleaning9 · Thin film formation
Partial recipeSource: Main

Route 7: Solvothermal

7 · General Methods

Metal precursorsZn(NO3)2.6H2O; 1.1 equiv relative to XDI
Linker precursorsPDI; 1 equiv
SolventsDMF
Additivesnone stated
Atmospherenot stated for powder route
Temperature130
Time4
Substrate orientationnot applicable
Oxidant / reductantnone stated
Work-upnot stated
Activationnot stated
Scalability contextBulk powder route reported only in summary form.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZn (NO3)2.6H2O1.1 molar equivalents7 · General Methods
LinkerPDI1 molar equivalent7 · General Methods
SolventDMFnot stated7 · General Methods
Complete recipeSource: Both

Route 8: Solvothermal

9 · Thin film formation

Metal precursorsZn(NO3)2.6H2O (0.11 mmol)
Linker precursorsPMDI (0.10 mmol)
SolventsDMF
AdditivesAlconox, ethanol and acetone used for FTO cleaning; KPF6 only for later electrochemistry, not synthesis
Atmospheredeaerated by bubbling argon for 10 min before sealing
Temperature130
Time4.5
Substrate orientationprecleaned FTO slides inserted with FTO side facing down
Oxidant / reductantnone stated
Work-upcooled to room temperature; films washed with DMF and sonicated 1 min to remove loosely bound powder
Activationsoaked in DMF until further use; no thermal/vacuum activation reported for films
Scalability contextFTO pieces were 2.5 x 1.1 cm2 in a 20 mL scintillation vial; no scale-up study reported
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZn (NO3)2.6H2O0.11 mmol9 · Thin film formation
LinkerPMDI0.10 mmol9 · Thin film formation
SolventDMFnot stated9 · Thin film formation
AdditiveAlconox (1%)used for FTO cleaning · 1%9 · Thin film formation
Solventethanolused for FTO cleaning9 · Thin film formation
Solventacetoneused for FTO cleaning9 · Thin film formation
Partial recipeSource: Main

Route 9: Solvothermal

7 · General Methods

Metal precursorsZn(NO3)2.6H2O; 1.1 equiv relative to XDI
Linker precursorsPMDI; 1 equiv
SolventsDMF
Additivesnone stated
Atmospherenot stated for powder route
Temperature130
Time4
Substrate orientationnot applicable
Oxidant / reductantnone stated
Work-upnot stated
Activationnot stated
Scalability contextBulk powder route reported only in summary form.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceZn (NO3)2.6H2O1.1 molar equivalents7 · General Methods
LinkerPMDI1 molar equivalent7 · General Methods
SolventDMFnot stated7 · General Methods