cMOF Evidence Base

Synthesis evidence

Nanosheets of Two-Dimensional Magnetic and Conducting Fe(II)/Fe(III) Mixed-Valence Metal-Organic Frameworks

Benmansour S., Abherve A., Gomez-Claramunt P. et al. · ACS Applied Materials and Interfaces · 2017 · 26210-26218

8 structured synthesis routes

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

Partial recipeSource: Both

Route 1: Drop Cast

S-8 · Delamination experiments · Figure S10

Solventsmethanol best; acetone also tested
AtmosphereDried with Ar after drop casting
Temperatureroom temperature
Time0.25 h sonication for best result; 30 s to 30 min tested
Substrate orientation300 nm SiO2/Si substrate
Work-upSuspension deposited onto SiO2/Si by drop casting and dried with Ar.
Scalability contextSimple wet delamination; concentration of suspension not reported.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Otherblack crystals of 1not specifiedS-8 · Delamination experiments · Figure S10
Solventmethanolnot specifiedS-8 · Delamination experiments · Figure S10
Complete recipeSource: Main

Route 2: Liquid Liquid Interface

p002 · Experimental Section

Metal precursors(NBu4)3[Fe(C6O4Cl2)3] and Fe(BF4)2.6H2O
Linker precursorsphenazine; chloranilato ligands contained in [Fe(C6O4Cl2)3]3- precursor
Solventsacetonitrile, THF, water
AtmosphereOpen air chemicals; three degassed solutions sealed after layering
Temperatureroom temperature
Timeabout 3.5 months
Oxidant / reductantMixed Fe(III) precursor complex and Fe(II) salt used to ensure both oxidation states
Work-upBlack shiny microcrystalline solid isolated; detailed washing/drying not separately specified.
Activationnone reported
Scalability contextReported larger-quantity polycrystalline synthesis, 0.382 g product, 98.5% yield.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal Source(NBu4)3[Fe(C6O4Cl2)3]0.40 g, 0.3 mmol · in 50 mL acetonitrilep002 · Experimental Section
Linkerphenazine1.30 g, 9 mmol · in 50 mL THFp002 · Experimental Section
Metal SourceFe(BF4)2.6H2O1.42 g, 4.2 mmol · in 50 mL waterp002 · Experimental Section
Complete recipeSource: Main

Route 3: Liquid Liquid Interface

p002 · Experimental Section

Metal precursors[PEtPh3]3[Fe(C6O4Cl2)3] and Fe(BF4)2.6H2O
Linker precursorsphenazine; chloranilato ligands contained in [Fe(C6O4Cl2)3]3- precursor
Solventsacetonitrile, THF, water
AtmosphereOpen air chemicals; degassed solutions sealed after layering
Temperatureroom temperature
Timeabout 2 months
Oxidant / reductantMixed Fe(III) precursor complex and Fe(II) salt used to ensure both oxidation states
Work-upCrystals suitable for X-ray diffraction were filtered and air-dried.
Activationnone reported for pristine crystals
Scalability contextSingle-crystal growth on 0.01 mmol Fe(III) precursor scale; separate larger-scale polycrystalline route reported.
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
Metal Source[PEtPh3]3[Fe(C6O4Cl2)3]15.5 mg, 0.01 mmol · in acetonitrile (4.5 mL)p002 · Experimental Section
Linkerphenazine54 mg, 0.3 mmol · in THF (2 mL)p002 · Experimental Section
Metal SourceFe(BF4)2.6H2O55 mg, 0.16 mmol · in water (2.5 mL)p002 · Experimental Section
Solventacetonitrile4.5 mLp002 · Experimental Section
SolventTHF2 mLp002 · Experimental Section
Solventwater2.5 mLp002 · Experimental Section
Partial recipeSource: SI

Route 4: Other

S-12 · Water removal · Figure S16

SolventsTHF
AtmosphereVacuum at 100 C after THF exchange
Temperature100 C evacuation
Timenot specified
Work-upTHF-exchanged sample submitted to vacuum at 100 C to remove THF and some H2O.
Activationvacuum at 100 C; removal incomplete
Scalability contextPost-synthetic guest exchange/removal experiment; no masses, THF exposure time or vacuum duration reported.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
SolventTHFnot specifiedS-12 · Water removal · Figure S16
Othercompound 1not specifiedS-12 · Water removal · Figure S16
Partial recipeSource: Both

Route 5: Drop Cast

S-8 · Delamination experiments · Figure S10

Solventsmethanol best; acetone also tested
AtmosphereDried with Ar after drop casting
Temperatureroom temperature
Time0.25 h sonication for best result; 30 s to 30 min tested
Substrate orientation300 nm SiO2/Si substrate
Work-upSuspension deposited onto SiO2/Si by drop casting and dried with Ar.
Scalability contextSimple wet delamination; concentration of suspension not reported.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Otherblack crystals of 2not specifiedS-8 · Delamination experiments · Figure S10
Solventmethanolnot specifiedS-8 · Delamination experiments · Figure S10
Complete recipeSource: Main

Route 6: Liquid Liquid Interface

p002 · Experimental Section

Metal precursors(NBu4)3[Fe(C6O4Br2)3] and Fe(BF4)2.6H2O
Linker precursorsphenazine; bromanilato ligands contained in [Fe(C6O4Br2)3]3- precursor
Solventsacetonitrile, THF, water
AtmosphereOpen air chemicals; three degassed solutions sealed after layering
Temperatureroom temperature
Timeabout 3.5 months
Oxidant / reductantMixed Fe(III) precursor complex and Fe(II) salt used to ensure both oxidation states
Work-upBlack shiny microcrystalline solid isolated; detailed washing/drying not separately specified.
Activationnone reported
Scalability contextReported larger-quantity polycrystalline synthesis, 0.748 g product, 80.0% yield.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal Source(NBu4)3[Fe(C6O4Br2)3]1.00 g, 0.6 mmol · in 100 mL acetonitrilep002 · Experimental Section
Linkerphenazine2.60 g, 18 mmol · in 100 mL THFp002 · Experimental Section
Metal SourceFe(BF4)2.6H2O2.84 g, 8.4 mmol · in 100 mL waterp002 · Experimental Section
Partial recipeSource: Main

Route 7: Liquid Liquid Interface

p002 · Experimental Section · Figure S2

Metal precursors[PEtPh3]3[Fe(C6O4Br2)3] and Fe(BF4)2.6H2O
Linker precursorsphenazine; bromanilato ligands contained in [Fe(C6O4Br2)3]3- precursor
Solventsacetonitrile, THF, water
AtmosphereOpen air chemicals; degassed layered solutions as in compound 1
Temperatureroom temperature
Timeabout 2 months by analogy to compound 1; exact time not restated
Oxidant / reductantMixed Fe(III) precursor complex and Fe(II) salt used to ensure both oxidation states
Work-upSingle crystals obtained; detailed filtering/drying as for compound 1 is implied but not restated.
Activationnone reported
Scalability contextSingle-crystal route using 0.01 mmol Br Fe(III) precursor; larger-scale polycrystalline route separately reported.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal Source[PEtPh3]3[Fe(C6O4Br2)3]18.2 mg, 0.01 mmolp002 · Experimental Section · Figure S2
Linkerphenazine54 mg, 0.3 mmol by analogy to compound 1 · in THF (2 mL) by analogyp002 · Experimental Section · Figure S2
Metal SourceFe(BF4)2.6H2O55 mg, 0.16 mmol by analogy to compound 1 · in water (2.5 mL) by analogyp002 · Experimental Section · Figure S2
Partial recipeSource: SI

Route 8: Other

S-12-S-13 · Water removal · Figure S17

SolventsTHF
AtmosphereVacuum at 100 C after THF exchange
Temperature100 C evacuation
Timenot specified
Work-upTHF-exchanged sample submitted to vacuum at 100 C to remove THF and some H2O.
Activationvacuum at 100 C; removal incomplete
Scalability contextPost-synthetic guest exchange/removal experiment; no masses, THF exposure time or vacuum duration reported.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
SolventTHFnot specifiedS-12-S-13 · Water removal · Figure S17
Othercompound 2not specifiedS-12-S-13 · Water removal · Figure S17