Synthesis · Morphological control of a metal-organic framework for single-crystal electronic device fabrication

11 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

4 · Results and discussions

Metal precursorsnone

Linker precursorsH4TTFTB

SolventsDMF, water, and ethanol mixture

Additivesnone

Atmospherenot stated

Temperature25

Time24

Substrate orientationnot applicable

Oxidant / reductantnone stated

Work-upnot isolated as a separate synthetic target in main text; H4TTFTB crystals appear from mother liquor/high-ligand mixture

Activationnot stated

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H4TTFTB	43 mg, 89.5 mmol in Zn-10 trial	4 · Results and discussions
Solvent	DMF	0.525 mL in SI Zn-10	4 · Results and discussions
Solvent	ethanol	0.175 mL + 0.35 mL in SI Zn-10	4 · Results and discussions
Solvent	water	0.35 mL in SI Zn-10	4 · Results and discussions

Complete recipeSource: Both

Route 2: Solvothermal

3 · Synthesis of Zn2(TTFTB)

Metal precursorsZn(NO3)2.6H2O

Linker precursorsH4TTFTB

Solvents0.35 mL water + 0.35 mL ethanol metal solution; 0.525 mL DMF + 0.175 mL ethanol linker solution

Additivesnone

Atmospherenot stated

Temperature65

Time72 h hold after approx. 30 min heating

Substrate orientationnot applicable

Oxidant / reductantnone stated

Work-uptop solution decanted; solid soaked in DMF 3 times and ethanol 3 times

Activationvacuum oven, 40 deg C, 24 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	13.8 mg, 66.5 mmol	3 · Synthesis of Zn2(TTFTB)
Linker	H4TTFTB	8.6 mg, 17.9 mmol	3 · Synthesis of Zn2(TTFTB)
Solvent	water	0.35 mL in metal solution	3 · Synthesis of Zn2(TTFTB)
Solvent	ethanol	0.35 mL in metal solution; 0.175 mL in linker solution	3 · Synthesis of Zn2(TTFTB)
Solvent	DMF	0.525 mL in linker solution	3 · Synthesis of Zn2(TTFTB)

Complete recipeSource: Both

Route 3: Solvothermal

5 · Synthesis of Zn2(TTFTB)

Metal precursorsZn(NO3)2.6H2O

Linker precursorsH4TTFTB

SolventsH4TTFTB first in 0.525 mL DMF + 0.175 mL ethanol, then 0.35 mL water + 0.35 mL ethanol added; Zn(NO3)2.6H2O in 0.05 mL water added after 24 h

Additivessequential ligand crystallisation before Zn2+ addition

Atmospherenot stated

Temperature25 then 85

Time24 h at 25 deg C before Zn addition; then 12 h hold at 85 deg C with 10 h heat/cool ramps

Substrate orientationnot applicable

Oxidant / reductantnone stated

Work-uptop solution decanted; powder soaked in DMF 3 times and ethanol 3 times

Activationvacuum oven, 40 deg C, 24 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	13.8 mg, 66.5 mmol	5 · Synthesis of Zn2(TTFTB)
Linker	H4TTFTB	43 mg, 89.5 mmol	5 · Synthesis of Zn2(TTFTB)
Solvent	DMF	0.525 mL	5 · Synthesis of Zn2(TTFTB)
Solvent	ethanol	0.175 mL + 0.35 mL	5 · Synthesis of Zn2(TTFTB)
Solvent	water	0.35 mL + 0.05 mL	5 · Synthesis of Zn2(TTFTB)

Complete recipeSource: Both

Route 4: Solvothermal

3 · Synthesis of Zn2(TTFTB)

Metal precursorsZn(NO3)2.6H2O

Linker precursorsH4TTFTB

Solventsbase Zn-1 solvent mixture plus another 1 mL water

Additivesadditional water

Atmospherenot stated

Temperature65

Time72 h hold; heated to 65 deg C in 10 h and cooled to 30 deg C in 10 h

Substrate orientationnot applicable

Oxidant / reductantnone stated

Work-uptop solution decanted; solid soaked in DMF 3 times and ethanol 3 times

Activationvacuum oven, 40 deg C, 24 h

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	13.8 mg, 66.5 mmol	3 · Synthesis of Zn2(TTFTB)
Linker	H4TTFTB	8.6 mg, 17.9 mmol	3 · Synthesis of Zn2(TTFTB)
Solvent	water	0.35 mL in metal solution	3 · Synthesis of Zn2(TTFTB)
Solvent	ethanol	0.35 mL in metal solution; 0.175 mL in linker solution	3 · Synthesis of Zn2(TTFTB)
Solvent	DMF	0.525 mL in linker solution	3 · Synthesis of Zn2(TTFTB)
Solvent	water	additional 1 mL	3 · Synthesis of Zn2(TTFTB)

Complete recipeSource: Both

Route 5: Solvothermal

4 · Synthesis of Zn2(TTFTB)

Metal precursorsZn(NO3)2.6H2O

Linker precursorsH4TTFTB

Solventsbase Zn-2 solvent mixture with additional 1 mL water

Additivesadditional water

Atmospherenot stated

Temperature65

Time72 h hold; heated on hotplate in around 30 min and naturally cooled

Substrate orientationnot applicable

Oxidant / reductantnone stated

Work-uptop solution decanted; solid soaked in DMF 3 times and ethanol 3 times

Activationvacuum oven, 40 deg C, 24 h

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	13.8 mg, 66.5 mmol	4 · Synthesis of Zn2(TTFTB)
Linker	H4TTFTB	8.6 mg, 17.9 mmol	4 · Synthesis of Zn2(TTFTB)
Solvent	water	0.35 mL in metal solution	4 · Synthesis of Zn2(TTFTB)
Solvent	ethanol	0.35 mL in metal solution; 0.175 mL in linker solution	4 · Synthesis of Zn2(TTFTB)
Solvent	DMF	0.525 mL in linker solution	4 · Synthesis of Zn2(TTFTB)
Solvent	water	additional 1 mL	4 · Synthesis of Zn2(TTFTB)

Complete recipeSource: Both

Route 6: Solvothermal

4 · Synthesis of Zn2(TTFTB)

Metal precursorsZn(NO3)2.6H2O

Linker precursorsH4TTFTB

Solvents0.35 mL water + 0.35 mL ethanol metal solution; 0.525 mL DMF + 0.175 mL ethanol linker solution

Additivesnone

Atmospherenot stated

Temperature65

Time24 h hold after around 30 min heating

Substrate orientationnot applicable

Oxidant / reductantnone stated

Work-uptop solution decanted; powder soaked in DMF 3 times and ethanol 3 times

Activationvacuum oven, 40 deg C, 24 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	13.8 mg, 66.5 mmol	4 · Synthesis of Zn2(TTFTB)
Linker	H4TTFTB	8.6 mg, 17.9 mmol	4 · Synthesis of Zn2(TTFTB)
Solvent	water	0.35 mL in metal solution	4 · Synthesis of Zn2(TTFTB)
Solvent	ethanol	0.35 mL in metal solution; 0.175 mL in linker solution	4 · Synthesis of Zn2(TTFTB)
Solvent	DMF	0.525 mL in linker solution	4 · Synthesis of Zn2(TTFTB)

Complete recipeSource: Both

Route 7: Solvothermal

4 · Synthesis of Zn2(TTFTB)

Metal precursorsZn(NO3)2.6H2O

Linker precursorsH4TTFTB

Solvents0.35 mL water + 0.35 mL ethanol metal solution; 0.525 mL DMF + 0.175 mL ethanol linker solution

Additivesnone

Atmospherenot stated

Temperature85

Time72 h hold; heated to 85 deg C in 10 h and cooled to 30 deg C in 10 h

Substrate orientationnot applicable

Oxidant / reductantnone stated

Work-uptop solution decanted; powder soaked in DMF 3 times and ethanol 3 times

Activationvacuum oven, 40 deg C, 24 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	13.8 mg, 66.5 mmol	4 · Synthesis of Zn2(TTFTB)
Linker	H4TTFTB	8.6 mg, 17.9 mmol	4 · Synthesis of Zn2(TTFTB)
Solvent	water	0.35 mL in metal solution	4 · Synthesis of Zn2(TTFTB)
Solvent	ethanol	0.35 mL in metal solution; 0.175 mL in linker solution	4 · Synthesis of Zn2(TTFTB)
Solvent	DMF	0.525 mL in linker solution	4 · Synthesis of Zn2(TTFTB)

Complete recipeSource: Both

Route 8: Solvothermal

4 · Synthesis of Zn2(TTFTB)

Metal precursorsZn(NO3)2.6H2O

Linker precursorsH4TTFTB

Solvents0.35 mL water + 0.35 mL methanol metal solution; 0.525 mL DMF + 0.175 mL ethanol + 0.175 mL water + 0.3 mL acetonitrile linker solution

Additivesmethanol and acetonitrile solvent change

Atmospherenot stated

Temperature65

Time72 h hold; heated to 65 deg C in 10 h and cooled to 30 deg C in 10 h

Substrate orientationnot applicable

Oxidant / reductantnone stated

Work-uptop solution decanted; powder soaked in DMF 3 times and ethanol 3 times

Activationvacuum oven, 40 deg C, 24 h

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	13.8 mg, 66.5 mmol	4 · Synthesis of Zn2(TTFTB)
Linker	H4TTFTB	8.6 mg, 17.9 mmol	4 · Synthesis of Zn2(TTFTB)
Solvent	water	0.35 mL metal solution; 0.175 mL linker solution	4 · Synthesis of Zn2(TTFTB)
Solvent	methanol	0.35 mL	4 · Synthesis of Zn2(TTFTB)
Solvent	DMF	0.525 mL	4 · Synthesis of Zn2(TTFTB)
Solvent	ethanol	0.175 mL	4 · Synthesis of Zn2(TTFTB)
Solvent	acetonitrile	0.3 mL	4 · Synthesis of Zn2(TTFTB)

Complete recipeSource: Both

Route 9: Solvothermal

5 · Synthesis of Zn2(TTFTB)

Metal precursorsZn(NO3)2.6H2O

Linker precursorsH4TTFTB

Solvents0.35 mL water + 0.35 mL ethanol metal solution; 0.525 mL DMF + 0.175 mL ethanol linker solution

Additives100 uL acetic acid

Atmospherenot stated

Temperature65

Time72 h hold after around 30 min heating

Substrate orientationnot applicable

Oxidant / reductantnone stated

Work-uptop solution decanted; powder soaked in DMF 3 times and ethanol 3 times

Activationvacuum oven, 40 deg C, 24 h

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	13.8 mg, 66.5 mmol	5 · Synthesis of Zn2(TTFTB)
Linker	H4TTFTB	8.6 mg, 17.9 mmol	5 · Synthesis of Zn2(TTFTB)
Solvent	water	0.35 mL in metal solution	5 · Synthesis of Zn2(TTFTB)
Solvent	ethanol	0.35 mL in metal solution; 0.175 mL in linker solution	5 · Synthesis of Zn2(TTFTB)
Solvent	DMF	0.525 mL in linker solution	5 · Synthesis of Zn2(TTFTB)
Acid	acetic acid	100 uL	5 · Synthesis of Zn2(TTFTB)

Complete recipeSource: Both

Route 10: Solvothermal

5 · Synthesis of Zn2(TTFTB)

Metal precursorsZn(NO3)2.6H2O

Linker precursorsH4TTFTB

Solvents0.35 mL water + 0.35 mL ethanol metal solution; 0.525 mL DMF + 0.175 mL ethanol linker solution

Additivesincreased Zn(NO3)2.6H2O amount

Atmospherenot stated

Temperature75

Time72 h hold; heated to 75 deg C in 10 h and cooled to 30 deg C in 10 h

Substrate orientationnot applicable

Oxidant / reductantnone stated

Work-uptop solution decanted; powder soaked in DMF 3 times and ethanol 3 times

Activationvacuum oven, 40 deg C, 24 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	138 mg, 665 mmol	5 · Synthesis of Zn2(TTFTB)
Linker	H4TTFTB	8.6 mg, 17.9 mmol	5 · Synthesis of Zn2(TTFTB)
Solvent	water	0.35 mL	5 · Synthesis of Zn2(TTFTB)
Solvent	ethanol	0.35 mL metal solution; 0.175 mL linker solution	5 · Synthesis of Zn2(TTFTB)
Solvent	DMF	0.525 mL	5 · Synthesis of Zn2(TTFTB)

Complete recipeSource: Main

Route 11: Solvothermal

5 · Synthesis of Zn2(TTFTB)

Metal precursorsZn(NO3)2.6H2O

Linker precursorsH4TTFTB

Solvents0.35 mL water + 0.35 mL ethanol metal solution; 0.525 mL DMF + 0.175 mL EtOH linker solution

Additiveshigh H4TTFTB concentration; metal-to-ligand ratio reduced to 1:5

Atmospherenot stated

Temperature75

Time72 h hold; heated to 75 deg C in 10 h and cooled to 30 deg C in 10 h

Substrate orientationnot applicable

Oxidant / reductantnone stated

Work-upvacuum filtration; rinsed with DMF eight times and EtOH eight times to remove first type crystals

Activationvacuum oven, 40 deg C, 24 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	13.8 mg, 66.5 mmol	5 · Synthesis of Zn2(TTFTB)
Linker	H4TTFTB	43 mg, 89.5 mmol	5 · Synthesis of Zn2(TTFTB)
Solvent	water	0.35 mL	5 · Synthesis of Zn2(TTFTB)
Solvent	ethanol	0.35 mL metal solution; 0.175 mL linker solution	5 · Synthesis of Zn2(TTFTB)
Solvent	DMF	0.525 mL	5 · Synthesis of Zn2(TTFTB)