Synthesis · Highly conducting two-dimensional copper(i) 4-hydroxythiophenolate network

6 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Other

3 · Notes and references, Synthesis of CuAT

Metal precursorsCuHT (50 mg, 0.26 mmol of OH group)

Linker precursorsCuHT framework precursor

SolventsDMF (5 mL)

Additivesacetic anhydride (100 uL, 1.06 mmol; 4 equivalents)

Atmospherenitrogen

Temperatureroom temperature

Time24

Work-upall powder disappeared; resultant light green solution used directly for electrical measurement; dried under vacuum to light green rubbery solid

Activationvacuum drying after reaction

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	CuHT	50 mg, 0.26 mmol of OH group	3 · Notes and references, Synthesis of CuAT
Solvent	DMF	5 mL	3 · Notes and references, Synthesis of CuAT
Additive	acetic anhydride	100 uL, 1.06 mmol · 4 equivalents	3 · Notes and references, Synthesis of CuAT

Partial recipeSource: Both

Route 2: Drop Cast

2 · FET discussion · Fig. 2(ii)

Metal precursorsCuAT solid sample

Solventsmethanol

Atmospheremeasured in MBraun nitrogen glove box; oxygen and moisture below 0.1 ppm

Temperatureroom temperature

Time>12 h ultrasonication before casting (SI general procedure)

Substrate orientationbottom-contact FET

Work-upCuAT in methanol drop-cast on bottom-contact FET

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	CuAT	Not specified	2 · FET discussion · Fig. 2(ii)
Solvent	methanol	Not specified	2 · FET discussion · Fig. 2(ii)

Partial recipeSource: SI

Route 3: Drop Cast

4 · FET Device Fabrication and Charge Mobility Measurement

Metal precursorsCuHT solid sample

Solventsmethanol

Atmospheremeasured in MBraun nitrogen glove box; oxygen and moisture below 0.1 ppm

Temperatureroom temperature

Time>12 h ultrasonication before casting

Substrate orientationbottom-contact FET

Work-upCuHT suspension in methanol ultrasonicated for more than 12 h and drop-cast on patterned bottom-contact FET device

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	CuHT	Not specified	4 · FET Device Fabrication and Charge Mobility Measurement
Solvent	methanol	Not specified	4 · FET Device Fabrication and Charge Mobility Measurement

Partial recipeSource: SI

Route 4: Other

3 · Four-point probe measurements

Metal precursorsCuHT powder

Atmospheretransferred to nitrogen glove box with <0.1 ppm water and oxygen after pellet preparation

Temperatureroom temperature

Work-uppressed under 8 tons to form 1 cm diameter pellets

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	CuHT powder	Not specified	3 · Four-point probe measurements

Complete recipeSource: Main

Route 5: Other

3 · Notes and references, Synthesis of CuHT

Metal precursorsCopper(I) oxide (0.500 g, 3.5 mmol)

Linker precursors4-hydroxythiophenol / 4-mercaptophenol (0.882 g, 7.0 mmol)

Solventsabsolute ethanol (50 mL)

Atmospheredegassed by three freeze-pump-thaw cycles and filled with nitrogen

Temperatureethanol reflux; main-text short description says dried at 40 C, footnote says dried at 70 C

Time24

Oxidant / reductantCu2O acts as Cu(I) source

Work-upcooled to room temperature; suction filtration; washed with ethanol (5 x 10 mL), water (3 x 10 mL), ethanol (2 x 10 mL), diethyl ether (2 x 10 mL)

Activationdried under vacuum for 12 h; footnote reports 70 C and main text reports vacuum oven at 40 C

Scalability contextIsolated yield 1.221 g, 92%.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	4-hydroxythiophenol	0.882 g, 7.0 mmol	3 · Notes and references, Synthesis of CuHT
Metal Source	Copper(I) oxide	0.500 g, 3.5 mmol	3 · Notes and references, Synthesis of CuHT
Solvent	absolute ethanol	50 mL	3 · Notes and references, Synthesis of CuHT

Partial recipeSource: Main

Route 6: Other

2 · structure discussion

Metal precursorsCu(I) source, same manner as CuHT

Linker precursors3-hydroxythiophenolate precursor / 3-hydroxythiophenol, same manner as CuHT

Solventsnot specified; same manner as CuHT implies ethanol

Atmospherenot specified; same manner as CuHT implies nitrogen after degassing

Temperaturenot specified; same manner as CuHT implies reflux

Timenot specified; same manner as CuHT implies 24 h

Work-upnot specified

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(I) source, same manner as CuHT	Not specified	2 · structure discussion
Linker	3-hydroxythiophenol / 3-hydroxythiophenolate precursor	Not specified	2 · structure discussion