cMOF Evidence Base

Synthesis evidence

Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal-Organic Framework

Darago L.E., Aubrey M.L., Yu C.J. et al. · Journal of the American Chemical Society · 2015 · 15703-15711

3 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Hydrothermal

2 · Experimental Section

Metal precursorsFe(SO4).7H2O, 121 mg (0.434 mmol)
Linker precursors2,5-diaminobenzoquinone, 20.0 mg (0.144 mmol), hydrolysed in situ to dhbq2-
Solvents3.0 mL deionised water
AdditivesTetrabutylammonium bromide, 250 mg (0.775 mmol); concentrated HCl to pH 3.0
AtmosphereReaction suspension degassed by four freeze-pump-thaw cycles; tube flame-sealed; product recovered in N2 glovebag.
Temperature120
Time24
Work-upCooled to room temperature; black cubic crystals recovered by vacuum filtration inside N2 glovebag.
ActivationDried by heating solid crystals at 150 C under reduced pressure for 1 h.
Scalability contextThick-walled sealed borosilicate tube route; yield 21.0 mg, 43%.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Linker2,5-diaminobenzoquinone20.0 mg (0.144 mmol)2 · Experimental Section
Metal SourceFe(SO4).7H2O121 mg (0.434 mmol)2 · Experimental Section
Additivetetrabutylammonium bromide250 mg (0.775 mmol)2 · Experimental Section
Solventdeionised water3.0 mL2 · Experimental Section
Acidconcentrated HClto pH 3.02 · Experimental Section
Complete recipeSource: Main

Route 2: Other

2 · Experimental Section

Metal precursorsFramework 1, 50 mg (0.049 mmol)
Linker precursorsPreformed dhbq framework 1
Solvents3.0 mL THF suspension of 1; 2.0 mL THF for Na-naphthalenide
AtmosphereAr-atmosphere glovebox for grinding, reduction and subsequent manipulations.
Temperatureroom temperature
Time12
Oxidant / reductantNa-naphthalenide prepared from naphthalene, 6.3 mg (0.049 mmol), over roughly 10-fold excess sodium metal in THF for 3 h.
Work-upFiltered Na-naphthalenide added dropwise; product recovered by vacuum filtration, washed with 2 x 2.0 mL THF.
ActivationDried for 1 h under reduced pressure.
Scalability contextYield 46.0 mg, 96%; two independently synthesised batches gave identical elemental and ICP analyses.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Other(NBu4)2FeIII2(dhbq)3 (1)50 mg (0.049 mmol)2 · Experimental Section
SolventTHF3.0 mL + 2.0 mL2 · Experimental Section
ReductantNa-naphthalenide from naphthalene and sodium metal6.3 mg (0.049 mmol) naphthalene; roughly 10-fold excess sodium metal2 · Experimental Section
Complete recipeSource: SI

Route 3: Other

S-3 · Experimental Details

Metal precursorsFramework 1, 53.3 mg (0.053 mmol)
Linker precursorsPreformed dhbq framework 1
Solvents3.0 mL THF suspension of 1; 2.0 mL THF for Na-naphthalenide
AtmosphereAr-atmosphere glovebox.
Temperatureroom temperature
Time12
Oxidant / reductantNa-naphthalenide prepared from naphthalene, 27.0 mg (0.211 mmol), over roughly 10-fold excess sodium metal in THF for 3 h.
Work-upFiltered Na-naphthalenide added drop-wise; product recovered by vacuum filtration and washed with 2 x 2.0 mL THF.
ActivationDried for 1 h under reduced pressure.
Scalability contextPutative formula because elemental analysis was unsuccessful.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Other(NBu4)2FeIII2(dhbq)3 (1)53.3 mg (0.053 mmol)S-3 · Experimental Details
SolventTHF3.0 mL + 2.0 mLS-3 · Experimental Details
ReductantNa-naphthalenide from naphthalene and sodium metal27.0 mg (0.211 mmol) naphthalene; roughly 10-fold excess sodium metalS-3 · Experimental Details