Synthesis · Redox-Active 1D Coordination Polymers of Iron-Sulfur Clusters

8 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Solvothermal

3946 · Experimental Section - [Fe4S4(BDT)2][TBA]2 (1)

Metal precursors[Fe4S4(SPh)4][TBA]2 (192 mg, 0.15 mmol)

Linker precursors1,4-benzenedithiol (43 mg, 0.30 mmol)

SolventsDMF, total 15 mL

Additives[Li][CF3SO3] (117 mg, 0.75 mmol)

AtmosphereInert/dry N2 conditions per General Methods

Temperature140

Time48

Work-upCentrifuged; washed with DMF (4 x 2 mL) and THF (3 x 2 mL); dried under vacuum.

ActivationDried under vacuum

Scalability context24 mL vial scale; isolated yield 102 mg, 61%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	[Fe4S4(SPh)4][TBA]2	192 mg, 0.15 mmol	3946 · Experimental Section - [Fe4S4(BDT)2][TBA]2 (1)
Linker	1,4-benzenedithiol	43 mg, 0.30 mmol	3946 · Experimental Section - [Fe4S4(BDT)2][TBA]2 (1)
Solvent	DMF	12 mL + 3 mL	3946 · Experimental Section - [Fe4S4(BDT)2][TBA]2 (1)
Additive	[Li][CF3SO3]	117 mg, 0.75 mmol	3946 · Experimental Section - [Fe4S4(BDT)2][TBA]2 (1)

Complete recipeSource: Main

Route 2: Solvothermal

3946 · Experimental Section - [Fe4S4(BDT)2][TMA]2 (2)

Metal precursors[Fe4S4(SPh)4][TMA]2 (140 mg, 0.15 mmol)

Linker precursors1,4-benzenedithiol (43 mg, 0.30 mmol)

SolventsMeCN, total 15 mL

Additives[Li][CF3SO3] (936 mg, 6.0 mmol)

AtmosphereInert/dry N2 conditions per General Methods

Temperature100

Time48

Work-upCentrifuged; washed with MeCN (4 x 2 mL); dried under vacuum.

ActivationDried under vacuum

Scalability context24 mL vial scale; isolated yield 68 mg, 58%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	[Fe4S4(SPh)4][TMA]2	140 mg, 0.15 mmol	3946 · Experimental Section - [Fe4S4(BDT)2][TMA]2 (2)
Linker	1,4-benzenedithiol	43 mg, 0.30 mmol	3946 · Experimental Section - [Fe4S4(BDT)2][TMA]2 (2)
Solvent	MeCN	9 mL + 6 mL	3946 · Experimental Section - [Fe4S4(BDT)2][TMA]2 (2)
Additive	[Li][CF3SO3]	936 mg, 6.0 mmol	3946 · Experimental Section - [Fe4S4(BDT)2][TMA]2 (2)

Complete recipeSource: Main

Route 3: Other

3946 · Experimental Section - Treatment with [R4N][PF6] · Table S1

Metal precursorsCompound 1 (0.05 mmol, 55 mg)

SolventsDMF/MeCN (5 mL)

Additives[TBA][PF6] (0.25 mmol, 67 mg)

AtmosphereGlovebox

Temperature100

Timeovernight

Work-upCentrifuged; washed with fresh DMF/MeCN and THF; dried for hours under vacuum.

ActivationDried under vacuum

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Compound 1	0.05 mmol, 55 mg	3946 · Experimental Section - Treatment with [R4N][PF6] · Table S1
Additive	[TBA][PF6]	0.25 mmol, 67 mg	3946 · Experimental Section - Treatment with [R4N][PF6] · Table S1

Complete recipeSource: Main

Route 4: Other

3946 · Experimental Section - Oxidative Doping Experiments · Figure S16

Metal precursorsCompound 1 (0.05 mmol, 56 mg)

SolventsMeCN (4 mL) and MeOH (1 mL)

AdditivesExcess [TMA][Br] (5 equiv, 0.25 mmol, 38 mg)

AtmosphereInert atmosphere implied by General Methods

Temperatureroom temperature

Timeovernight

Oxidant / reductant[Fc][BF4] (0.5 equiv, 0.025 mmol, 7 mg)

Work-upCentrifuged; washed with MeCN until wash solvent was colourless; dried under vacuum.

ActivationDried under vacuum

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Compound 1	0.05 mmol, 56 mg	3946 · Experimental Section - Oxidative Doping Experiments · Figure S16
Oxidant	[Fc][BF4]	0.5 equiv, 0.025 mmol, 7 mg	3946 · Experimental Section - Oxidative Doping Experiments · Figure S16
Additive	[TMA][Br]	5 equiv, 0.25 mmol, 38 mg	3946 · Experimental Section - Oxidative Doping Experiments · Figure S16

Complete recipeSource: Main

Route 5: Other

3946 · Experimental Section - Reductive Doping Experiments · Figure S15; Table 1

Metal precursorsCompound 1 (0.05 mmol, 56 mg)

SolventsTHF (5 mL)

AdditivesExcess [Li][CF3SO3] (5 equiv, 0.25 mmol, 39 mg)

AtmosphereInert atmosphere implied by General Methods

Temperatureroom temperature

Timeovernight

Oxidant / reductantCoCp*2 (0.5 equiv, 0.025 mmol, 8 mg)

Work-upCentrifuged; washed with THF until wash solvent was colourless; dried under vacuum.

ActivationDried under vacuum

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Compound 1	0.05 mmol, 56 mg	3946 · Experimental Section - Reductive Doping Experiments · Figure S15; Table 1
Reductant	*CoCp2**	0.5 equiv, 0.025 mmol, 8 mg	3946 · Experimental Section - Reductive Doping Experiments · Figure S15; Table 1
Additive	[Li][CF3SO3]	5 equiv, 0.25 mmol, 39 mg	3946 · Experimental Section - Reductive Doping Experiments · Figure S15; Table 1
Solvent	THF	5 mL	3946 · Experimental Section - Reductive Doping Experiments · Figure S15; Table 1

Complete recipeSource: Main

Route 6: Other

3946 · Experimental Section - Oxidative Doping Experiments · Figure S18

Metal precursorsCompound 2 (0.05 mmol, 39 mg)

SolventsMeCN (4 mL) and MeOH (1 mL)

AdditivesExcess [TMA][Br] (5 equiv, 0.25 mmol, 38 mg)

AtmosphereInert atmosphere implied by General Methods

Temperatureroom temperature

Timeovernight

Oxidant / reductant[Fc][BF4] (0.5 equiv, 0.025 mmol, 7 mg)

Work-upCentrifuged; washed with MeCN until wash solvent was colourless; dried under vacuum.

ActivationDried under vacuum

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Compound 2	0.05 mmol, 39 mg	3946 · Experimental Section - Oxidative Doping Experiments · Figure S18
Oxidant	[Fc][BF4]	0.5 equiv, 0.025 mmol, 7 mg	3946 · Experimental Section - Oxidative Doping Experiments · Figure S18
Additive	[TMA][Br]	5 equiv, 0.25 mmol, 38 mg	3946 · Experimental Section - Oxidative Doping Experiments · Figure S18

Complete recipeSource: Main

Route 7: Other

3946 · Experimental Section - Reductive Doping Experiments · Figure S17; Table 1

Metal precursorsCompound 2 (0.05 mmol, 39 mg)

SolventsTHF (5 mL)

AdditivesExcess [Li][CF3SO3] (5 equiv, 0.25 mmol, 39 mg)

AtmosphereInert atmosphere implied by General Methods

Temperatureroom temperature

Timeovernight

Oxidant / reductantCoCp*2 (0.5 equiv, 0.025 mmol, 8 mg)

Work-upCentrifuged; washed with THF until wash solvent was colourless; dried under vacuum.

ActivationDried under vacuum

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Compound 2	0.05 mmol, 39 mg	3946 · Experimental Section - Reductive Doping Experiments · Figure S17; Table 1
Reductant	*CoCp2**	0.5 equiv, 0.025 mmol, 8 mg	3946 · Experimental Section - Reductive Doping Experiments · Figure S17; Table 1
Additive	[Li][CF3SO3]	5 equiv, 0.25 mmol, 39 mg	3946 · Experimental Section - Reductive Doping Experiments · Figure S17; Table 1
Solvent	THF	5 mL	3946 · Experimental Section - Reductive Doping Experiments · Figure S17; Table 1

Complete recipeSource: Main

Route 8: Other

3946 · Experimental Section - Chemical Reduction of 2 in Solution · Figures S24, S25, S27, S41, S42

Metal precursorsCompound 2 in DMF (27 mL, 34 mg, 0.043 mmol)

SolventsDMF; Et2O for precipitation

AtmosphereInert atmosphere implied by General Methods

Temperatureroom temperature

Timeovernight

Oxidant / reductant[Na][C12H8] solution (0.5 equiv, 1.24 mL, 0.022 mmol)

Work-upReduced solid precipitated by equal volume Et2O, centrifuged, washed with THF (4 x 2 mL), dried under vacuum.

ActivationDried under vacuum

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Compound 2	34 mg, 0.043 mmol · 27 mL DMF	3946 · Experimental Section - Chemical Reduction of 2 in Solution · Figures S24, S25, S27, S41, S42
Reductant	[Na][C12H8]	0.5 equiv, 1.24 mL, 0.022 mmol	3946 · Experimental Section - Chemical Reduction of 2 in Solution · Figures S24, S25, S27, S41, S42
Solvent	DMF	27 mL	3946 · Experimental Section - Chemical Reduction of 2 in Solution · Figures S24, S25, S27, S41, S42
Solvent	Et2O	equal volume	3946 · Experimental Section - Chemical Reduction of 2 in Solution · Figures S24, S25, S27, S41, S42