Synthesis · Solvent-controlled ion-coupled charge transport in microporous metal chalcogenides

3 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Other

SI p.S4 · Synthetic Procedures

Metal precursorsanhydrous iron(II) chloride (0.050 g, 0.40 mmol); TMA4Ge4S10 precursor (0.18 g, 0.20 mmol)

Linker precursorsTMA4Ge4S10 germanium sulfide cluster precursor

SolventsN2-sparged DI water (4 mL for FeCl2, 8 mL for TMA4Ge4S10); sparged DI water, ethanol, hexanes washes

AdditivesTMA+ supplied by TMA4Ge4S10 precursor

AtmospherePositive nitrogen atmosphere; N2-sparged water; stored under positive N2

Temperatureroom temperature

Time~12

Work-upIron solution added dropwise over ~2 min; bright-orange solid washed sequentially with sparged DI water (15 mL x2), ethanol (15 mL x2), and hexanes (15 mL x2).

ActivationDried with a stream of nitrogen.

Scalability contextSmall batch solution synthesis; no scale-up assessment.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	anhydrous iron(II) chloride	0.050 g, 0.40 mmol	SI p.S4 · Synthetic Procedures
Other	TMA4Ge4S10	0.18 g, 0.20 mmol	SI p.S4 · Synthetic Procedures
Solvent	N2-sparged DI water	4 mL and 8 mL	SI p.S4 · Synthetic Procedures
Solvent	ethanol wash	15 mL x2	SI p.S4 · Synthetic Procedures
Solvent	hexanes wash	15 mL x2	SI p.S4 · Synthetic Procedures

Complete recipeSource: Both

Route 2: Other

SI p.S4 · Synthetic Procedures

Metal precursorszinc(II) nitrate hexahydrate (0.12 g, 0.40 mmol); TMA4Ge4S10 precursor (0.18 g, 0.20 mmol)

Linker precursorsTMA4Ge4S10 germanium sulfide cluster precursor

SolventsDI water (4 mL for zinc nitrate, 8 mL for TMA4Ge4S10); DI water wash

AdditivesTMA+ supplied by TMA4Ge4S10 precursor

AtmosphereAmbient conditions after synthesis; no inert atmosphere specified

Temperatureroom temperature reaction; 150 C drying

Time~12 h reaction; ~12 h drying

Work-upZinc solution added dropwise over ~2 min; white solid washed with DI water (15 mL x3).

ActivationDried in fixed-temperature oven at 150 C for ~12 h.

Scalability contextSmall batch solution synthesis; no scale-up assessment.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	zinc(II) nitrate hexahydrate	0.12 g, 0.40 mmol	SI p.S4 · Synthetic Procedures
Other	TMA4Ge4S10	0.18 g, 0.20 mmol	SI p.S4 · Synthetic Procedures
Solvent	DI water	4 mL and 8 mL; 15 mL x3 wash	SI p.S4 · Synthetic Procedures

Complete recipeSource: SI

Route 3: Solvothermal

SI p.S4 · Synthetic Procedures

Metal precursorsgermanium powder (1 g, 13.76 mmol)

Linker precursorssulfur powder (1.77 g, 6.88 mmol)

Solventswater (7.44 g, 412.8 mmol); acetone used for precipitation; acetone, hot toluene, and hexanes washes

Additivestetramethylammonium hydroxide pentahydrate (4.99 g, 27.5 mmol)

Atmospheresealed Teflon Parr bomb; storage under ambient conditions

Temperature150

Time15

Work-upVacuum filtered to remove unreacted Ge; ~500 mL acetone added; white powder washed with acetone (20 mL x3), hot toluene (20 mL x3), and hexanes (20 mL x3).

ActivationDried overnight under dynamic vacuum.

Scalability contextBatch in Parr bomb; no scale-up assessment.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	germanium powder	1 g, 13.76 mmol	SI p.S4 · Synthetic Procedures
Other	sulfur powder	1.77 g, 6.88 mmol	SI p.S4 · Synthetic Procedures
Solvent	water	7.44 g, 412.8 mmol	SI p.S4 · Synthetic Procedures
Base	tetramethylammonium hydroxide pentahydrate	4.99 g, 27.5 mmol	SI p.S4 · Synthetic Procedures
Solvent	acetone	~500 mL precipitation; 20 mL x3 wash	SI p.S4 · Synthetic Procedures
Solvent	hot toluene	20 mL x3 wash	SI p.S4 · Synthetic Procedures
Solvent	hexanes	20 mL x3 wash	SI p.S4 · Synthetic Procedures