Synthesis · Two-dimensional conductive metal-organic framework with 2,3,6,7,14,15-triptycenehexathiol (TCHT) ligand: synthesis, structure, electrical conductivity and CO2RR activity

7 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Drop Cast

S3-S4 · Electrocatalytic Performance Measurement for the CO2RR

SolventsTHF; ethanol

AdditivesMaxsorb porous carbon; 5 wt% Nafion dispersion

Atmospherenot specified for loading/electrode preparation

Temperature60

Timeovernight drying; 30 min sonication for ink

Substrate orientationgas diffusion electrode

Work-upLoad Cu-BHT on Maxsorb analogously; dry under vacuum at 60 C overnight; prepare catalyst ink with Nafion and ethanol; spray to GDE; vacuum-dry.

ActivationVacuum drying at 60 C overnight before and after GDE ink spraying.

Scalability contextComparator composite mass ratio Cu-BHT:Maxsorb approximately 1:3.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-BHT	4.92 mg	S3-S4 · Electrocatalytic Performance Measurement for the CO2RR
Additive	Maxsorb	14.76 mg	S3-S4 · Electrocatalytic Performance Measurement for the CO2RR
Solvent	THF	not specified	S3-S4 · Electrocatalytic Performance Measurement for the CO2RR
Additive	Nafion dispersion	10 uL per 3 mg catalyst ink · 5 wt%	S3-S4 · Electrocatalytic Performance Measurement for the CO2RR
Solvent	ethanol	300 uL per 3 mg catalyst ink	S3-S4 · Electrocatalytic Performance Measurement for the CO2RR

Vague recipeSource: Main

Route 2: Unknown

25725 · Chemicals

Linker precursorsBHT

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Linker	benzenehexathiol (BHT)	Not specified	25725 · Chemicals

Complete recipeSource: Main

Route 3: Other

25726 · Synthesis of Cu-TCHT · Scheme 1c

Metal precursorscopper(II) acetate monohydrate

Linker precursorsTCHT

Solventsdichloromethane; methanol

Atmospherenitrogen atmosphere except filtration; all solutions nitrogen-bubbled before use

Temperatureroom temperature

Timeovernight

Work-upImmediate brown-black precipitate; stirred overnight; filtered under atmospheric condition.

Scalability contextReported isolated mass 53.2 mg.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TCHT	38.0 mg, 0.086 mmol	25726 · Synthesis of Cu-TCHT · Scheme 1c
Solvent	dichloromethane	25 mL	25726 · Synthesis of Cu-TCHT · Scheme 1c
Metal Source	copper(II) acetate monohydrate	50.9 mg, 0.26 mmol	25726 · Synthesis of Cu-TCHT · Scheme 1c
Solvent	methanol	30 mL	25726 · Synthesis of Cu-TCHT · Scheme 1c

Complete recipeSource: SI

Route 4: Drop Cast

S3-S4 · Electrocatalytic Performance Measurement for the CO2RR

SolventsTHF; ethanol

AdditivesMaxsorb porous carbon; 5 wt% Nafion dispersion

Atmospherenot specified for loading/electrode preparation

Temperature60

Timeovernight drying; 30 min sonication for ink

Substrate orientationgas diffusion electrode

Work-upLoad Cu-TCHT on Maxsorb by THF addition and 3 min sonication; dry under vacuum at 60 C overnight; mix 3 mg catalyst with Nafion/ethanol by ultrasonic bath for 30 min; spray ink with airbrush; vacuum-dry at 60 C overnight.

ActivationVacuum drying at 60 C overnight before and after GDE ink spraying.

Scalability contextComposite mass ratio Cu-TCHT:Maxsorb approximately 1:3.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-TCHT	5.41 mg	S3-S4 · Electrocatalytic Performance Measurement for the CO2RR
Additive	Maxsorb	16.23 mg	S3-S4 · Electrocatalytic Performance Measurement for the CO2RR
Solvent	THF	5 mL	S3-S4 · Electrocatalytic Performance Measurement for the CO2RR
Additive	Nafion dispersion	10 uL · 5 wt%	S3-S4 · Electrocatalytic Performance Measurement for the CO2RR
Solvent	ethanol	300 uL	S3-S4 · Electrocatalytic Performance Measurement for the CO2RR

Complete recipeSource: Main

Route 5: Other

25725 · Synthesis of HBTC

Linker precursorstriptycene

Solventsanhydrous dichloromethane

Additivesiron powder; bromine; saturated NaHCO3 quench trap; saturated aqueous sodium sulfite quench

Atmosphereconstant nitrogen flow

Temperature-30

Time48

Oxidant / reductantbromine

Work-upQuench with saturated sodium sulfite solution; suction filtration; wash with methanol until filtrate colourless.

Scalability contextReported yield 1945 mg, 66.8%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	triptycene	1020 mg, 4.0 mmol	25725 · Synthesis of HBTC
Solvent	anhydrous dichloromethane	20 mL plus 50 mL for bromine dilution	25725 · Synthesis of HBTC
Additive	iron powder	100 mg	25725 · Synthesis of HBTC
Oxidant	bromine	1.35 mL, 26.2 mmol	25725 · Synthesis of HBTC

Complete recipeSource: Main

Route 6: Other

25726 · Synthesis of HMTTC · Scheme 2

Metal precursorscopper(I) iodide used as reagent

Linker precursorsHBTC

Solventsdimethyl sulfoxide; dichloromethane; hexane

Additives1,4-diazabicyclo[2.2.2]octane (DABCO); aqueous NaOH; MgSO4; Celite

Atmospherenot specified for microwave step

Temperature160

Time15

Oxidant / reductantcopper(I) iodide

Work-upAdd dichloromethane; wash three times with 0.35 M NaOH; dry over MgSO4; filter; remove solvent; load onto Celite; automated flash chromatography with dichloromethane and hexane; dry under reduced pressure.

Scalability contextReported yield 200 mg, 43%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HBTC	600 mg, 0.82 mmol	25726 · Synthesis of HMTTC · Scheme 2
Other	copper(I) iodide	1120 mg, 5.88 mmol	25726 · Synthesis of HMTTC · Scheme 2
Base	1,4-diazabicyclo[2.2.2]octane	450 mg, 4.00 mmol	25726 · Synthesis of HMTTC · Scheme 2
Solvent	dimethyl sulfoxide	20 mL	25726 · Synthesis of HMTTC · Scheme 2

Complete recipeSource: Main

Route 7: Other

25726 · Synthesis of TCHT · Scheme 2

Linker precursorsHMTTC

Solventsliquid ammonia; methanol; water; diethyl ether; dichloromethane

Additivesdilute hydrochloric acid

Atmospheredehydrated nitrogen atmosphere; all solutions nitrogen-bubbled; extraction in nitrogen glovebox

Temperature-78

Time3

Oxidant / reductantmetallic sodium Birch reduction

Work-upQuench slowly with methanol; evaporate ammonia; add water; wash three times with diethyl ether; add dilute HCl; filter precipitate in air; wash with water and methanol; extract with dichloromethane in nitrogen glovebox; remove solvent under anaerobic reduced pressure.

Scalability contextReported yield 490 mg, 81%.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HMTTC	980 mg, 1.35 mmol	25726 · Synthesis of TCHT · Scheme 2
Reductant	metallic sodium	1.1 g, 48 mmol	25726 · Synthesis of TCHT · Scheme 2
Solvent	liquid ammonia	50 mL	25726 · Synthesis of TCHT · Scheme 2
Solvent	methanol	20 mL	25726 · Synthesis of TCHT · Scheme 2