Synthesis · Humidity-Mediated Dual Ionic-Electronic Conductivity Enables High Sensitivity in MOF Chemiresistors

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

p007 / SI p.7 · S2.3

Metal precursorsCo(OAc)2.4H2O, 24.9 mg (0.1 mmol)

Linker precursorsH6HHTP, 16.2 mg (0.05 mmol)

Solvents1 mL DMF solution and 1 mL aqueous solution; DI water, DMF, and acetone washes

Temperature85

Time24

Work-upCooled to 25 C and washed via centrifugation twice with 50 mL DI water, DMF, and acetone

ActivationSensor films activated at 80 C for 30 min before sensing

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(OAc)2.4H2O	24.9 mg (0.1 mmol) · in 1 mL aqueous solution	p007 / SI p.7 · S2.3
Linker	H6HHTP	16.2 mg (0.05 mmol) · in 1 mL DMF	p007 / SI p.7 · S2.3

Complete recipeSource: SI

Route 2: Solvothermal

p007 / SI p.7 · S2.4

Metal precursorsCo(NO3)2.6H2O, 8.13 mg (0.0279 mmol)

Linker precursorsHATP.6HCl, 10 mg (0.0186 mmol)

SolventsDMF; water; DI water, DMF, and acetone washes

AdditivesNaOAc aqueous solution, 4 mL, 2 M

AtmosphereVial lid slightly open

Temperature65

Time2

Work-upStirred while heated, cooled to 25 C, washed via centrifugation twice with 50 mL DI water, DMF, and acetone

ActivationSensor films activated at 80 C for 30 min before sensing

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	8.13 mg (0.0279 mmol) · in 3 mL DMF	p007 / SI p.7 · S2.4
Linker	HATP.6HCl	10 mg (0.0186 mmol) · in 3 mL aqueous solution	p007 / SI p.7 · S2.4
Base	NaOAc aqueous solution	4 mL · 2 M	p007 / SI p.7 · S2.4

Complete recipeSource: SI

Route 3: Solvothermal

p006 / SI p.6 · S2.3

Metal precursorsCu(OAc)2.4H2O, 19.9 mg (0.1 mmol)

Linker precursorsH6HHTP, 16.2 mg (0.05 mmol)

Solvents1 mL DMF solution and 1 mL aqueous solution; DI water, DMF, and acetone washes

Temperature85

Time24

Work-upCooled to 25 C and washed via centrifugation twice with 50 mL DI water, DMF, and acetone

ActivationSensor films activated at 80 C for 30 min before sensing

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2.4H2O	19.9 mg (0.1 mmol) · in 1 mL aqueous solution	p006 / SI p.6 · S2.3
Linker	H6HHTP	16.2 mg (0.05 mmol) · in 1 mL DMF	p006 / SI p.6 · S2.3

Complete recipeSource: Both

Route 4: Solvothermal

p006 / SI p.6 · S2.2 Synthesis of Cu3(HHTT)2

Metal precursorsCuSO4.5H2O, 45 mg in 2.1 mL aqueous solution

Linker precursorsHHTT ligand, 50 mg in 0.9 mL DMF

Solventswater; DMF; DI water, DMF, and acetone workup

Temperature85

Time18

Work-upCooled to room temperature and washed via centrifugation twice with 50 mL DI water, DMF, and acetone respectively

ActivationDegassed at 120 C overnight for sorption; pre-activated at 120 C under flowing Ar for DRIFTS; pre-activated at 80 C under dry air for humidity PXRD

Scalability contextSmall-batch vial synthesis; no scale-up reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4.5H2O	45 mg · in 2.1 mL aqueous solution	p006 / SI p.6 · S2.2 Synthesis of Cu3(HHTT)2
Linker	HHTT ligand	50 mg · in 0.9 mL DMF solution	p006 / SI p.6 · S2.2 Synthesis of Cu3(HHTT)2
Solvent	water	2.1 mL solution	p006 / SI p.6 · S2.2 Synthesis of Cu3(HHTT)2
Solvent	DMF	0.9 mL solution plus wash solvent	p006 / SI p.6 · S2.2 Synthesis of Cu3(HHTT)2
Solvent	acetone	wash solvent	p006 / SI p.6 · S2.2 Synthesis of Cu3(HHTT)2

Partial recipeSource: Both

Route 5: Drop Cast

p013 / SI p.13 · Section S4 · Table S1

Metal precursorsPre-synthesised Cu3HHTT2 powder

Solventsslurry solvent not specified

AtmosphereDry air and analyte gases during sensing

Temperature80 C activation; room temperature sensing ca. 25 C

Time0.5 h activation

Substrate orientationAu-interdigitated electrodes, 150 um gap shown in Figure S7

Work-upDrop-cast films adjusted by number or volume of droplets; sensors installed in flow chamber

ActivationAs-prepared sensors activated at 80 C for 30 min before room-temperature gas sensing

Scalability contextUp to 16 sensors could be installed in the flow chamber.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3HHTT2 slurry	n = 0.2, 0.5, 1, 2, 4, 8, 12, and 16 droplet-equivalent films; 1 drop = 5 uL except reduced volumes · 2 mg/mL	p013 / SI p.13 · Section S4 · Table S1
Other	Au-interdigitated electrode	Not specified	p013 / SI p.13 · Section S4 · Table S1

Complete recipeSource: SI

Route 6: Solvothermal

p007 / SI p.7 · S2.4

Metal precursorsCuSO4.5H2O, 7 mg (0.028 mmol)

Linker precursorsHATP.6HCl, 10 mg (0.0186 mmol)

SolventsDMF; water; DI water, DMF, and acetone washes

AdditivesNa(OAc) aqueous solution, 4 mL, 2 mol reported

AtmosphereVial lid slightly open

Temperature65

Time2

Work-upSonicated 1 min, stirred while heated, cooled to 25 C, washed via centrifugation twice with 50 mL DI water, DMF, and acetone

ActivationSensor films activated at 80 C for 30 min before sensing

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4.5H2O	7 mg (0.028 mmol) · in 3 mL DMF	p007 / SI p.7 · S2.4
Linker	HATP.6HCl	10 mg (0.0186 mmol) · in 3 mL aqueous solution	p007 / SI p.7 · S2.4
Base	Na(OAc) aqueous solution	4 mL · 2 mol (raw SI text)	p007 / SI p.7 · S2.4

Complete recipeSource: SI

Route 7: Other

p006 / SI p.6 · S2.1 Synthesis of HHTT

Linker precursors5,6-Dimethoxyanthranil; ammonium acetate; pyridine hydrochloride

Solventsacetic acid; sulfolane; DI water and methanol washes

Additivesammonium acetate; pyridine hydrochloride

AtmosphereN2 atmosphere

Temperaturereflux; cooled to 25 C

Time96 h for hexamethoxy precursor; 3 h for HHTT deprotection

Work-upDark brown solids washed with DI water and methanol by centrifugation; HHTT product washed with DI water by centrifugation

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	5,6-Dimethoxyanthranil	4.28 g (11.95 mmol)	p006 / SI p.6 · S2.1 Synthesis of HHTT
Additive	ammonium acetate	12.3 g (79.8 mmol)	p006 / SI p.6 · S2.1 Synthesis of HHTT
Acid	acetic acid	15 mL	p006 / SI p.6 · S2.1 Synthesis of HHTT
Solvent	sulfolane	75 mL	p006 / SI p.6 · S2.1 Synthesis of HHTT
Linker	2,3,7,8,12,13-Hexamethoxytricycloquinazoline	0.810 g (1.620 mmol)	p006 / SI p.6 · S2.1 Synthesis of HHTT
Additive	pyridine hydrochloride	27.4 g (237.06 mmol)	p006 / SI p.6 · S2.1 Synthesis of HHTT

Complete recipeSource: SI

Route 8: Hydrothermal

p006 / SI p.6 · S2.3

Metal precursorsNi(OAc)2.4H2O, 24.9 mg (0.1 mmol)

Linker precursorsH6HHTP, 16.2 mg (0.05 mmol)

Solventsaqueous solutions; DI water, DMF, and acetone washes

Temperature85

Time24

Work-upCooled to 25 C and washed via centrifugation twice with 50 mL DI water, DMF, and acetone

ActivationSensor films activated at 80 C for 30 min before sensing

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	24.9 mg (0.1 mmol) · in 1 mL aqueous solution	p006 / SI p.6 · S2.3
Linker	H6HHTP	16.2 mg (0.05 mmol) · in 1 mL aqueous solution	p006 / SI p.6 · S2.3

Complete recipeSource: SI

Route 9: Solvothermal

p007 / SI p.7 · S2.4

Metal precursorsNi(OAc)2.4H2O, 6.94 mg (0.0278 mmol)

Linker precursorsHATP.6HCl, 10 mg (0.0186 mmol)

SolventsDMF; water; DI water, DMF, and acetone washes

AdditivesNaOAc aqueous solution, 2 mL, 2 M

AtmosphereVial lid slightly open

Temperature65

Time2

Work-upStirred while heated, cooled to 25 C, washed via centrifugation twice with 50 mL DI water, DMF, and acetone

ActivationSensor films activated at 80 C for 30 min before sensing

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	6.94 mg (0.0278 mmol) · in 1.5 mL DMF	p007 / SI p.7 · S2.4
Linker	HATP.6HCl	10 mg (0.0186 mmol) · in 1.5 mL aqueous solution	p007 / SI p.7 · S2.4
Base	NaOAc aqueous solution	2 mL · 2 M	p007 / SI p.7 · S2.4