Synthesis · Electron-Conductive Metal-Organic Framework, Fe(dhbq)(dhbq = 2,5-Dihydroxy-1,4-benzoquinone): Coexistence of Microporosity and Solid-State Redox Activity

5 structured synthesis routes

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

Partial recipeSource: Both

Route 1: Other

2 · Characterization and Instrumental Procedures

Metal precursorsFe(dhbq) active material

Linker precursorsdhbq in Fe(dhbq)

Solvents1 M LiClO4 in EC/DEC 1:1 used as electrolyte during cell assembly

Additivesacetylene black (40 wt%); PTFE (10 wt%)

Atmospherenot specified for grinding/assembly

Temperatureroom temperature (cell fabrication; not explicitly specified)

Timenot specified

Substrate orientationlithium foil anode and Celgard separator in CR2032 coin cell

Oxidant / reductantlithium electrochemical counter/reference during measurement

Work-upFe(dhbq), AB and PTFE ground with agate mortar; cathode composite stacked with lithium foil, Celgard and electrolyte; cell filled and sealed.

Activationnone reported after mixing

Scalability contextComposition reported, but electrode loading, pressing dimensions and cell-assembly atmosphere are not stated.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Fe(dhbq)	50 wt%	2 · Characterization and Instrumental Procedures
Additive	acetylene black (AB)	40 wt%	2 · Characterization and Instrumental Procedures
Additive	PTFE	10 wt%	2 · Characterization and Instrumental Procedures
Electrolyte	LiClO4 in EC/DEC 1:1	full filled and sealed · 1 M	2 · Characterization and Instrumental Procedures

Partial recipeSource: Both

Route 2: Other

4 · Results and Discussion · Table 1; Figure S15

Metal precursorsFe(dhbq) active material

Linker precursorsdhbq in Fe(dhbq)

Solvents1 M LiClO4 in EC/DEC 1:1 electrolyte used during cell assembly

Additivesacetylene black and PTFE at variable ratios

Atmospherenot specified

Temperatureroom temperature (not explicitly specified)

Timenot specified

Substrate orientationCR2032 coin-cell configuration

Oxidant / reductantlithium foil anode during electrochemical testing

Work-upSame grinding and coin-cell assembly procedure as 50 wt% cathode; variable ratios reported for 10 wt% and 80 wt% Fe(dhbq) cases.

Activationnone reported after mixing

Scalability contextUsed for composition-dependence comparison; full electrode loading not reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Fe(dhbq)	10 wt% or 80 wt%	4 · Results and Discussion · Table 1; Figure S15
Additive	acetylene black (AB)	80 wt% or 10 wt%	4 · Results and Discussion · Table 1; Figure S15
Additive	PTFE	10 wt%	4 · Results and Discussion · Table 1; Figure S15

Partial recipeSource: Both

Route 3: Other

2 · Results and Discussion · Figure 3

Metal precursorsFe(dhbq)(H2O)2 precursor

Linker precursorsdhbq already incorporated in Fe(dhbq)(H2O)2

Solventsnone

Additivesnone

Atmospherenot explicitly specified for bulk activation; TGA performed under N2 gas flow

Temperatureup to 180 C inferred from TGA desolvation; exact activation temperature not stated

Timenot stated

Oxidant / reductantthermal dehydration/desolvation

Work-upLoss of two axial water molecules forms anhydrous Fe(dhbq); SEM appearance showed no significant change.

ActivationDehydration/desolvation of Fe(dhbq)(H2O)2; exact preparative activation protocol not fully reported.

Scalability contextNo explicit scale for dehydration step reported.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	Fe(dhbq)(H2O)2	not specified	2 · Results and Discussion · Figure 3

Complete recipeSource: SI

Route 4: Other

3 · III. Syntheses

Metal precursorsFeSO4.7H2O (640 mg, 2.3 mmol)

Linker precursorsH2dhbq (322 mg, 2.3 mmol)

SolventsWater: 100 mL FeSO4 solution plus 100 mL mixed H2dhbq/K2CO3 solution

AdditivesK2CO3 (317 mg, 2.3 mmol)

AtmosphereN2 atmosphere

Temperatureroom temperature (not explicitly specified)

Timeimmediate precipitation; drying time not specified

Oxidant / reductantNo deliberate oxidant/reductant; N2 used to suppress oxidation

Work-upPrecipitate formed immediately; solid filtered and dried to deep brown solid; yield 476 mg (90%).

ActivationNone reported for hydrated product; later dehydration gives Fe(dhbq).

Scalability context100 mL + 100 mL aqueous precipitation gives 476 mg product.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	FeSO4.7H2O	640 mg, 2.3 mmol	3 · III. Syntheses
Linker	H2dhbq	322 mg, 2.3 mmol	3 · III. Syntheses
Base	K2CO3	317 mg, 2.3 mmol	3 · III. Syntheses
Solvent	water	200 mL total	3 · III. Syntheses

Complete recipeSource: SI

Route 5: Air Liquid Interface

3 · III. Syntheses

Metal precursorsFeSO4.7H2O (140 mg, 0.5 mmol)

Linker precursors1,2,4,5-tetrahydroxybenzene (THB, 70 mg, 0.5 mmol), oxidised in situ to dhbq

SolventsWater, 30 mL FeSO4 solution

Atmosphereair

Temperatureroom temperature (not explicitly specified)

Time168

Oxidant / reductantAir/O2 oxidises THB to dhbq; THB also acts as reducing agent preventing Fe(II) oxidation.

Work-upPrecipitate collected; single crystals suitable for X-ray structure analysis selected by optical microscope.

ActivationNone reported for hydrated single crystals.

Scalability contextSlow process gave large single crystals but bulk solid contained an unidentified phase, so it was not used for property measurements.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	FeSO4.7H2O	140 mg, 0.5 mmol	3 · III. Syntheses
Reductant	1,2,4,5-tetrahydroxybenzene (THB)	70 mg, 0.5 mmol	3 · III. Syntheses
Oxidant	O2 from air	not quantified	3 · III. Syntheses
Solvent	water	30 mL	3 · III. Syntheses