Synthesis · Screening-Enabled Chemiresistive Moisture Sensing with Tetrathiafulvalene-Based Electrically Conductive Metal–Organic Frameworks

9 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Solvothermal

3 · Synthesis of Cd2(TTFTB) in aerobic conditions

Metal precursorsCd(NO3)2.4H2O (172 mg, 0.56 mmol)

Linker precursorsH4TTFTB (103 mg, 0.154 mmol)

Solvents6 mL water + 6 mL EtOH for metal solution; 6.3 mL DMF + 2.1 mL EtOH for linker solution; solvents deoxygenated

Atmosphereoxygen-free and water-compatible glovebox; aerobic-condition sample per authors' wording

Temperature75

Time72 h hold after 5 deg C/h heat ramp; cool to 30 deg C at 5 deg C/h

Oxidant / reductantdeoxygenated solvents; no explicit oxidant/reductant

Work-upTop solution decanted; crystals soaked in DMF 3 times and EtOH 3 times

ActivationDried in vacuum oven at 40 deg C for 24 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cd(NO3)2.4H2O	172 mg, 0.56 mmol	3 · Synthesis of Cd2(TTFTB) in aerobic conditions
Linker	H4TTFTB	103 mg, 0.154 mmol	3 · Synthesis of Cd2(TTFTB) in aerobic conditions
Solvent	water	6 mL · deoxygenated by freeze-pump-thaw	3 · Synthesis of Cd2(TTFTB) in aerobic conditions
Solvent	EtOH	8.1 mL total · deoxygenated	3 · Synthesis of Cd2(TTFTB) in aerobic conditions
Solvent	DMF	6.3 mL · deoxygenated	3 · Synthesis of Cd2(TTFTB) in aerobic conditions

Partial recipeSource: SI

Route 2: Unknown

2 · Materials

Metal precursorsnot specified for ordinary in-air Cd2(TTFTB) sample

Linker precursorsnot specified for ordinary in-air Cd2(TTFTB) sample

Solventsnot specified for ordinary in-air Cd2(TTFTB) sample

Atmosphereair; all synthesis in humid air unless otherwise specified

Scalability contextMain text states M2(TTFTB) can be grown as millimetre-scale single crystals under optimized literature conditions.

Complete recipeSource: SI

Route 3: Solvothermal

2 · Synthesis of Co2(TTFTB)

Metal precursorsCo(NO3)2.6H2O (77 mg, 0.27 mmol)

Linker precursorsH4TTFTB (50 mg, 0.073 mmol)

Solvents4 mL deionized water + 4 mL EtOH for metal solution; 6 mL DMF + 2 mL EtOH for linker solution

Atmospherehumid air unless otherwise specified

Temperature75

Time72 h hold after 10 h heat ramp; 10 h cool to 30 deg C

Oxidant / reductantspontaneous oxidation of TTF introduces TTF radical cations during/after framework formation

Work-upTop solution decanted; crystals soaked in DMF 3 times and EtOH 3 times

ActivationDried in vacuum oven at 40 deg C for 24 h

Scalability contextMillimetre-scale rod-like crystals reported for non-Zn analogues.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	77 mg, 0.27 mmol	2 · Synthesis of Co2(TTFTB)
Linker	H4TTFTB	50 mg, 0.073 mmol	2 · Synthesis of Co2(TTFTB)
Solvent	deionized water	4 mL	2 · Synthesis of Co2(TTFTB)
Solvent	EtOH	6 mL total	2 · Synthesis of Co2(TTFTB)
Solvent	DMF	6 mL	2 · Synthesis of Co2(TTFTB)

Complete recipeSource: SI

Route 4: Other

5 · Fabrication of pressed pellets devices · Figure S7

Metal precursorsas-synthesised M2(TTFTB) framework powders

Atmosphereambient pellet/device fabrication conditions not fully specified

Timepressed for 5 min

Substrate orientationpressed pellet transferred to glass slide with Ti/Au electrodes

Work-upground with agate mortar and pestle, pressed in 6 mm die at approximately 20 MPa, contacted with gold wires and carbon paste

Scalability contextPellet device fabrication applies to the M2(TTFTB) series.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	as-synthesised M2(TTFTB) powder	not specified	5 · Fabrication of pressed pellets devices · Figure S7

Complete recipeSource: SI

Route 5: Solvothermal

3 · Synthesis of Mn2(TTFTB)

Metal precursorsMn(NO3)2.xH2O (67 mg, approximately 0.27 mmol)

Linker precursorsH4TTFTB (50 mg, 0.073 mmol)

Solvents4 mL water + 4 mL EtOH for metal solution; 6 mL DMF + 2 mL EtOH for linker solution

Atmospherehumid air unless otherwise specified

Temperature75

Time72 h hold after 10 h heat ramp; 10 h cool to 30 deg C

Oxidant / reductantspontaneous oxidation of TTF introduces TTF radical cations during/after framework formation

Work-upTop solution decanted; crystals soaked in DMF 3 times and ethanol 3 times

ActivationDried in vacuum oven at 40 deg C for 24 h

Scalability contextMillimetre-scale rod-like crystals reported for non-Zn analogues.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Mn(NO3)2.xH2O	67 mg, approximately 0.27 mmol	3 · Synthesis of Mn2(TTFTB)
Linker	H4TTFTB	50 mg, 0.073 mmol	3 · Synthesis of Mn2(TTFTB)
Solvent	water	4 mL	3 · Synthesis of Mn2(TTFTB)
Solvent	EtOH	6 mL total	3 · Synthesis of Mn2(TTFTB)
Solvent	DMF	6 mL	3 · Synthesis of Mn2(TTFTB)

Complete recipeSource: SI

Route 6: Solvothermal

3-4 · Synthesis of Zn2(TTFTB) in aerobic conditions

Metal precursorsZn(NO3)2.6H2O (13.8 mg, 0.046 mmol)

Linker precursorsH4TTFTB (43 mg, 0.063 mmol)

Solvents0.35 mL water + 0.35 mL EtOH for metal solution; 0.525 mL DMF + 0.175 mL EtOH for linker solution; solvents deoxygenated

Atmosphereoxygen-free and water-compatible glovebox; aerobic-condition sample per authors' wording

Temperature85

Time72 h hold after 5 deg C/h heat ramp; cool to 30 deg C at 5 deg C/h

Oxidant / reductantdeoxygenated solvents; no explicit oxidant/reductant

Work-upTop solution decanted; crystals soaked in DMF 3 times and EtOH 3 times

ActivationDried in vacuum oven at 40 deg C for 24 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	13.8 mg, 0.046 mmol	3-4 · Synthesis of Zn2(TTFTB) in aerobic conditions
Linker	H4TTFTB	43 mg, 0.063 mmol	3-4 · Synthesis of Zn2(TTFTB) in aerobic conditions
Solvent	water	0.35 mL · deoxygenated by freeze-pump-thaw	3-4 · Synthesis of Zn2(TTFTB) in aerobic conditions
Solvent	EtOH	0.525 mL total · deoxygenated	3-4 · Synthesis of Zn2(TTFTB) in aerobic conditions
Solvent	DMF	0.525 mL · deoxygenated	3-4 · Synthesis of Zn2(TTFTB) in aerobic conditions

Partial recipeSource: SI

Route 7: Unknown

48163 · Why Is Zn2(TTFTB) Distinct?

Metal precursorsnot specified for ordinary in-air Zn2(TTFTB) sample

Linker precursorsnot specified for ordinary in-air Zn2(TTFTB) sample

Solventsnot specified for ordinary in-air Zn2(TTFTB) sample

Atmosphereair; all synthesis in humid air unless otherwise specified

Scalability contextUnder same synthetic conditions, Zn2(TTFTB) crystals are typically shorter than 100 um.

Complete recipeSource: SI

Route 8: Solvothermal

4 · Synthesis of Zn2(TTFTB) for micro/nanofabrication

Metal precursorsZn(NO3)2.6H2O (14.0 mg, 0.046 mmol)

Linker precursorsH4TTFTB (8.8 mg, 0.013 mmol)

Solvents1.35 mL water + 0.35 mL EtOH for metal solution; 0.525 mL DMF + 0.175 mL EtOH for linker solution

Atmospherehumid air unless otherwise specified

Temperature85

Time14

Work-upCrystals kept in reaction mixture and washed right before micro/nanofabrication by soaking in DMF 3 times and EtOH 3 times

ActivationNo separate drying/activation stated for crystals before micro/nanofabrication

Scalability contextRecipe tailored to small rods for micro/nanofabricated devices.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	14.0 mg, 0.046 mmol	4 · Synthesis of Zn2(TTFTB) for micro/nanofabrication
Linker	H4TTFTB	8.8 mg, 0.013 mmol	4 · Synthesis of Zn2(TTFTB) for micro/nanofabrication
Solvent	water	1.35 mL	4 · Synthesis of Zn2(TTFTB) for micro/nanofabrication
Solvent	EtOH	0.525 mL total	4 · Synthesis of Zn2(TTFTB) for micro/nanofabrication
Solvent	DMF	0.525 mL	4 · Synthesis of Zn2(TTFTB) for micro/nanofabrication

Complete recipeSource: SI

Route 9: Other

5 · Micro/nano fabrication of single-crystal device · Figure S18

Solventsacetone, IPA, deionized water cleaning; IPA suspension of crystals; acetone lift-off

AdditivesMMA and PMMA resists; AR-5350 photoresist for markers

Atmosphereambient fabrication conditions not fully specified

Temperature50 and 85 bake steps

Timewafer cleaning 5 min each solvent; pre-bake 10 min; MMA/PMMA bakes 6 min; lift-off 5 min

Substrate orientation1 cm x 1 cm silicon wafer / SiO2/Si substrate; Pt electrodes crossing rod-like Zn2(TTFTB) crystals

Work-upDeveloped in IPA/deionized water 3:1 for 8 s and IPA 30 s; Pt >250 nm sputtered; acetone lift-off; IPA rinse; 50 deg C bake

Scalability contextMicro/nano device processing; not bulk synthesis.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Solvent	acetone	Not specified	5 · Micro/nano fabrication of single-crystal device · Figure S18
Solvent	IPA	Not specified	5 · Micro/nano fabrication of single-crystal device · Figure S18
Additive	MMA	MMA(8.5)MAA EL 6	5 · Micro/nano fabrication of single-crystal device · Figure S18
Additive	PMMA	AR-P 672.045	5 · Micro/nano fabrication of single-crystal device · Figure S18
Other	Pt electrodes	>250 nm	5 · Micro/nano fabrication of single-crystal device · Figure S18