Synthesis · Two-Dimensional Conjugated Metal-Organic Frameworks with Large Pore Apertures and High Surface Areas for NO2 Selective Chemiresistive Sensing

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: Other

S4 · Synthesis of HNOTP and HAOTP.6HCl · Scheme S1

Linker precursorsHHTP; 1,2-difluoro-4,5-dinitrobenzene; HNOTP intermediate

SolventsDry DMF, methanol, ethanol, 1.0 M hydrochloric acid

AdditivesK2CO3; concentrated HCl

AtmosphereDegassed and filled with N2 for both HNOTP formation and HAOTP.6HCl reduction

Temperature100 for HNOTP; 90 for HAOTP.6HCl; dried at 60

Time48 for HNOTP; 12 for HAOTP.6HCl

Oxidant / reductantstannous chloride dihydrate as reductant for nitro reduction

Work-upDMF removed by rotary evaporation; methanol ultrasonic dispersion and filtration; acid dispersion/filtration; rinsed with HCl and methanol

ActivationVacuum dried at 60 deg C

Scalability contextReported isolated yields: HNOTP 554 mg, 68%; HAOTP.6HCl 136 mg, 80%.

Show 9 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP	324 mg, 1 mmol	S4 · Synthesis of HNOTP and HAOTP.6HCl · Scheme S1
Linker	1,2-difluoro-4,5-dinitrobenzene	816 mg, 4 mmol	S4 · Synthesis of HNOTP and HAOTP.6HCl · Scheme S1
Base	K2CO3	552 mg, 4 mmol	S4 · Synthesis of HNOTP and HAOTP.6HCl · Scheme S1
Solvent	dry N,N-dimethylformamide (DMF)	6 mL	S4 · Synthesis of HNOTP and HAOTP.6HCl · Scheme S1
Other	HNOTP	163 mg, 0.2 mmol	S4 · Synthesis of HNOTP and HAOTP.6HCl · Scheme S1
Reductant	stannous chloride dihydrate	3354 mg, 14.8 mmol	S4 · Synthesis of HNOTP and HAOTP.6HCl · Scheme S1
Solvent	ethanol	20 mL	S4 · Synthesis of HNOTP and HAOTP.6HCl · Scheme S1
Acid	concentrated HCl	8 mL	S4 · Synthesis of HNOTP and HAOTP.6HCl · Scheme S1
Acid	hydrochloric acid	1.0 M	S4 · Synthesis of HNOTP and HAOTP.6HCl · Scheme S1

Complete recipeSource: SI

Route 2: Other

S3 · Iodine doping of HIOTP-M · Figure S25

Additivesiodine vapour

Atmospheresealed vial with iodine

Temperature85

Time24

Oxidant / reductantiodine dopant

Work-upcooled to room temperature

Activationpressed into pellet for conductivity measurement

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	HIOTP-M (M=Ni or Cu)	50 mg	S3 · Iodine doping of HIOTP-M · Figure S25
Oxidant	iodine	1 g	S3 · Iodine doping of HIOTP-M · Figure S25

Complete recipeSource: Both

Route 3: Solvothermal

S6 · Synthesis of HIOTP-Cu · Scheme S2

Metal precursorscopper(ii) nitrate hydrate (32.8 mg)

Linker precursorsHAOTP.6HCl (40 mg)

SolventsDMF (5 mL) and water (3 mL)

Additivessodium bicarbonate (16.8 mg)

Atmospherenot specified for MOF step

Temperature60

Time72

Work-upcooled to room temperature, filtered, washed with DMF, water and acetone

Activationdried under vacuum at 85 deg C for 12 h

Scalability contextProduct amount 40.1 mg.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HAOTP.6HCl	40 mg	S6 · Synthesis of HIOTP-Cu · Scheme S2
Metal Source	copper(ii) nitrate hydrate	32.8 mg	S6 · Synthesis of HIOTP-Cu · Scheme S2
Solvent	DMF	5 mL	S6 · Synthesis of HIOTP-Cu · Scheme S2
Solvent	water	3 mL	S6 · Synthesis of HIOTP-Cu · Scheme S2
Base	sodium bicarbonate	16.8 mg	S6 · Synthesis of HIOTP-Cu · Scheme S2

Partial recipeSource: SI

Route 4: Drop Cast

S3 · Gas sensor characterization

Solventsisopropanol dispersion

Atmospherevacuum drying after drop-casting

Temperature60

Time1

Work-updrop-cast on home-made interdigital electrode with 100 um gaps

Activationdried at 60 deg C in vacuum for 1 h

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	HIOTP-M isopropanol dispersion	appropriate dispersion	S3 · Gas sensor characterization
Solvent	isopropanol	Not specified	S3 · Gas sensor characterization

Complete recipeSource: SI

Route 5: Other

S3 · Iodine doping of HIOTP-M · Figure S24

Additivesiodine vapour

Atmospheresealed vial with iodine

Temperature85

Time24

Oxidant / reductantiodine dopant

Work-upcooled to room temperature

Activationpressed into pellet for conductivity measurement

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	HIOTP-M (M=Ni or Cu)	50 mg	S3 · Iodine doping of HIOTP-M · Figure S24
Oxidant	iodine	1 g	S3 · Iodine doping of HIOTP-M · Figure S24

Complete recipeSource: Both

Route 6: Solvothermal

S6 · Synthesis of HIOTP-Ni · Scheme S2

Metal precursorsnickel nitrate hexahydrate (30.6 mg)

Linker precursorsHAOTP.6HCl (30 mg)

SolventsN,N-dimethylformamide (DMF, 10.5 mL) and water (1.5 mL)

Additivesaqueous ammonia (25-28%, 60 uL)

Atmospherenot specified for MOF step

Temperature85

Time36

Work-upcooled to room temperature, filtered, washed with DMF, water and acetone

Activationdried under vacuum at 120 deg C for 12 h

Scalability contextProduct amount 28.4 mg.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HAOTP.6HCl	30 mg	S6 · Synthesis of HIOTP-Ni · Scheme S2
Metal Source	nickel nitrate hexahydrate	30.6 mg	S6 · Synthesis of HIOTP-Ni · Scheme S2
Solvent	N,N-dimethylformamide (DMF)	10.5 mL	S6 · Synthesis of HIOTP-Ni · Scheme S2
Solvent	water	1.5 mL	S6 · Synthesis of HIOTP-Ni · Scheme S2
Base	aqueous ammonia	60 uL · 25% ~ 28%	S6 · Synthesis of HIOTP-Ni · Scheme S2

Partial recipeSource: SI

Route 7: Drop Cast

S3 · Gas sensor characterization

Solventsisopropanol dispersion

Atmospherevacuum drying after drop-casting

Temperature60

Time1

Work-updrop-cast on home-made interdigital electrode with 100 um gaps

Activationdried at 60 deg C in vacuum for 1 h

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	HIOTP-M isopropanol dispersion	appropriate dispersion	S3 · Gas sensor characterization
Solvent	isopropanol	Not specified	S3 · Gas sensor characterization

Vague recipeSource: Both

Route 8: Unknown

p004 · Sensing comparison · Figure S32

Vague recipeSource: Both

Route 9: Unknown

p004 · Sensing comparison · Figure S32