Synthesis · Electron delocalization and charge mobility as a function of reduction in a metal-organic framework

5 structured synthesis routes

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

Partial recipeSource: SI

Route 1: Other

main Methods p.9 · Bulk reduction of Fe2(BDP)3

Metal precursorsActivated Fe2(BDP)3

Linker precursorsBDP already incorporated in Fe2(BDP)3

SolventsTHF; 10 ml per Fe2(BDP)3 suspension

AdditivesNaphthalene, 10% molar excess in potassium naphthalenide solution

AtmosphereRigorous exclusion of air and water; inert atmosphere Ar/N2 gloveboxes and Schlenk techniques

Temperatureroom temperature

Time1-2 h addition plus overnight stirring

Oxidant / reductant0.1 M potassium naphthalenide in THF

Work-upSolid collected and repeatedly washed with THF until THF washes showed no naphthalene; K:Fe ratios confirmed by ICP-OES and EDS.

ActivationActivated Fe2(BDP)3 used; exact parent activation before reduction not specified.

Scalability contextBulk powder reductions target desired stoichiometries by measured aliquots of reductant.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	activated Fe2(BDP)3	weighed aliquots	main Methods p.9 · Bulk reduction of Fe2(BDP)3
Reductant	potassium naphthalenide	measured amounts to target stoichiometries · 0.1 M	main Methods p.9 · Bulk reduction of Fe2(BDP)3
Additive	naphthalene	10% molar excess	main Methods p.9 · Bulk reduction of Fe2(BDP)3
Solvent	THF	10 ml for suspension	main Methods p.9 · Bulk reduction of Fe2(BDP)3

Complete recipeSource: SI

Route 2: Other

main Methods p.9 · Electrochemical measurements · Fig. 3b

Metal precursorsFe2(BDP)3 powder

Linker precursorsBDP already incorporated in Fe2(BDP)3

SolventsTHF; propylene carbonate electrolyte

AdditivesSuper P, polyvinylidene fluoride, carbon cloth, K(TFSI)

AtmosphereArgon glovebox

Temperature180

Timeapproximately 2 h desolvation

Substrate orientationCarbon cloth working electrode

Oxidant / reductantPotassium metal reference/counter electrodes; K(TFSI) electrolyte

Work-upSlurry drop-cast onto carbon cloth, desolvated, loaded into T-cell.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Fe2(BDP)3	60 wt%	main Methods p.9 · Electrochemical measurements · Fig. 3b
Additive	Super P	30 wt%	main Methods p.9 · Electrochemical measurements · Fig. 3b
Additive	polyvinylidene fluoride	10 wt%	main Methods p.9 · Electrochemical measurements · Fig. 3b
Electrolyte	K(TFSI) in anhydrous propylene carbonate	0.1 M	main Methods p.9 · Electrochemical measurements · Fig. 3b

Blocked Missing Si recipeSource: Both

Route 3: Unknown

main Methods p.9 · General considerations

AtmosphereAir- and water-free handling used unless otherwise specified

ActivationActivated Fe2(BDP)3 used for reduction, but parent synthesis/activation recipe is not reproduced.

Partial recipeSource: SI

Route 4: Drop Cast

main Methods p.10 · Single-crystal FET and four-point device fabrication · Figs. S16-S18

Metal precursorsFe2(BDP)3 microcrystals

Linker precursorsBDP already incorporated in Fe2(BDP)3

SolventsAcetonitrile

AdditivesPt/C deposited contact pads

AtmosphereSEM/FIB processing; subsequent reductions handled in dinitrogen glovebox

Substrate orientationFET substrates with 200 nm silicon dioxide; interdigitated microelectrodes

Work-upMicrocrystals micro-manipulated between prefabricated electrodes; Pt/C pads deposited by electron-beam-induced deposition.

Scalability contextSingle-crystal device fabrication is manual/micromanipulated.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Fe2(BDP)3 microcrystals	0.1 wt% dispersion	main Methods p.10 · Single-crystal FET and four-point device fabrication · Figs. S16-S18
Solvent	acetonitrile	Not specified	main Methods p.10 · Single-crystal FET and four-point device fabrication · Figs. S16-S18
Additive	Pt/C pads	Not specified	main Methods p.10 · Single-crystal FET and four-point device fabrication · Figs. S16-S18

Complete recipeSource: SI

Route 5: Other

main Methods p.10 · Sequential reduction and measurement of single-crystal Fe2(BDP)3 FETs · Fig. S15

Metal precursorsFe2(BDP)3 single-microcrystal FET devices plus excess Fe2(BDP)3 powder

Linker precursorsBDP already incorporated in Fe2(BDP)3

Solvents50 ml THF; toluene used to dissolve polystyrene protective coating

AdditivesPolystyrene in toluene protective coating; pierced aluminium foil housing

AtmosphereDinitrogen glovebox for reduction and coating

Temperatureroom temperature

Time1 h agitation plus overnight standing; 20 min toluene soak between cycles

Substrate orientationMicroelectrode-array FET chips

Oxidant / reductantAbout 20 ml freshly prepared 0.07 M potassium naphthalenide solution

Work-upChips rinsed five times with THF; bulk aliquot analysed by EDS; chips coated with polystyrene for transfer; cycle repeated.

Scalability contextStepwise reduction performed on devices and excess bulk powder in a 100 ml jar.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Fe2(BDP)3 FET devices	Not specified	main Methods p.10 · Sequential reduction and measurement of single-crystal Fe2(BDP)3 FETs · Fig. S15
Other	bulk Fe2(BDP)3 powder	300 mg	main Methods p.10 · Sequential reduction and measurement of single-crystal Fe2(BDP)3 FETs · Fig. S15
Solvent	THF	50 ml	main Methods p.10 · Sequential reduction and measurement of single-crystal Fe2(BDP)3 FETs · Fig. S15
Reductant	potassium naphthalenide	about 20 ml · 0.07 M	main Methods p.10 · Sequential reduction and measurement of single-crystal Fe2(BDP)3 FETs · Fig. S15
Additive	polystyrene in toluene	two drops, repeated twice	main Methods p.10 · Sequential reduction and measurement of single-crystal Fe2(BDP)3 FETs · Fig. S15