Synthesis · A Pyrazine-Based 2D Conductive Metal-Organic Framework for Efficient Lithium Storage†

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: Other

p004 / S3 · S1.3 Synthesis of Compounds · Scheme S1

Linker precursorscompound 1; tetraaminophenyl tetrahydrochloride

SolventsMeOH/AcOH (80 mL/240 mL); DCM extraction; DCM:EA = 10:1 chromatography

Additivestriethylamine, KOH, NaHCO3, anhydrous MgSO4

Atmosphereventilated three times and protected with nitrogen

Temperature130

Time12

Work-upNeutralised with KOH and NaHCO3, extracted with DCM, dried over MgSO4, purified by silica gel chromatography.

Scalability context1.0 g compound 1 scale; 85% yield.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	compound 1	1.0 g (3.0 mmol)	p004 / S3 · S1.3 Synthesis of Compounds · Scheme S1
Linker	tetraaminophenyl tetrahydrochloride	400 mg (1.4 mmol)	p004 / S3 · S1.3 Synthesis of Compounds · Scheme S1
Solvent	MeOH	80 mL	p004 / S3 · S1.3 Synthesis of Compounds · Scheme S1
Solvent	AcOH	240 mL	p004 / S3 · S1.3 Synthesis of Compounds · Scheme S1
Base	triethylamine	20 mL	p004 / S3 · S1.3 Synthesis of Compounds · Scheme S1

Complete recipeSource: SI

Route 2: Other

p004 / S3 · S1.3 Synthesis of Compounds · Scheme S1

Linker precursorsTPQ-8OCH3

Solventsdry DCM; ice water quench; water wash

Additivespure boron tribromide

Atmospherenitrogen atmosphere

Temperature-28 then room temperature

Time1 h at -28 C, then overnight at room temperature

Oxidant / reductantBBr3 demethylation reagent

Work-upPoured into ice water to quench excess BBr3; filtered; washed with water until neutral.

Scalability context1.0 g TPQ-8OCH3 scale; 90% yield.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TPQ-8OCH3	1.0 g (1.35 mmol)	p004 / S3 · S1.3 Synthesis of Compounds · Scheme S1
Solvent	dry DCM	75 mL	p004 / S3 · S1.3 Synthesis of Compounds · Scheme S1
Additive	pure boron tribromide	5 mL	p004 / S3 · S1.3 Synthesis of Compounds · Scheme S1

Complete recipeSource: SI

Route 3: Other

p005 / S4 · S1.3 Synthesis of Compounds · Scheme S2

Linker precursorsTPQ-8OCH3

SolventsDCM; nitromethane; DCM and H2O washing

AdditivesFeCl3

Atmospherenitrogen protection

Temperatureroom temperature

Time3

Oxidant / reductantFeCl3 oxidative cyclodehydrogenation reagent

Work-upFiltration and washing with DCM and H2O until filtrate was colourless.

Scalability context500 mg TPQ-8OCH3 scale; 95% yield.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TPQ-8OCH3	500 mg (0.70 mmol)	p005 / S4 · S1.3 Synthesis of Compounds · Scheme S2
Solvent	DCM	50 mL	p005 / S4 · S1.3 Synthesis of Compounds · Scheme S2
Oxidant	FeCl3	1.0 g	p005 / S4 · S1.3 Synthesis of Compounds · Scheme S2
Solvent	nitromethane	5 mL	p005 / S4 · S1.3 Synthesis of Compounds · Scheme S2

Complete recipeSource: SI

Route 4: Other

p005 / S4 · S1.3 Synthesis of Compounds · Scheme S2

Linker precursorsTPQG-8OCH3

Solventsdry DCM; ice water; water washing

Additivespure boron tribromide

Atmospherenitrogen atmosphere

Temperature-28 then room temperature

Time1 h at -28 C, then overnight at room temperature

Oxidant / reductantBBr3 demethylation reagent

Work-upAdded dropwise to ice water; DCM removed by reduced-pressure distillation; extracted and washed with water until neutral.

Scalability context500 mg TPQG-8OCH3 scale; 92% yield.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TPQG-8OCH3	500 mg (0.69 mmol)	p005 / S4 · S1.3 Synthesis of Compounds · Scheme S2
Solvent	dry DCM	170 mL	p005 / S4 · S1.3 Synthesis of Compounds · Scheme S2
Additive	pure boron tribromide	3 mL	p005 / S4 · S1.3 Synthesis of Compounds · Scheme S2

Complete recipeSource: Main

Route 5: Other

p005 / 1695 · Experimental: The digestion of TPQG-Cu-MOF · Figure S12

Metal precursorsTPQG-Cu-MOF

Solvents2 mol/L hydrochloric acid solution; water washes

AdditivesHCl

Atmospherenot specified

Temperatureroom temperature

Time48

Work-upSonicate to disperse, immerse for 2 d, filter, wash with water several times, vacuum dry overnight at room temperature.

Scalability context20 mg digestion scale.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	TPQG-Cu-MOF	20 mg	p005 / 1695 · Experimental: The digestion of TPQG-Cu-MOF · Figure S12
Acid	hydrochloric acid solution	10 mL · 2 mol/L	p005 / 1695 · Experimental: The digestion of TPQG-Cu-MOF · Figure S12

Complete recipeSource: Main

Route 6: Drop Cast

p005 / 1695 · Experimental: The preparation of half-cell

Metal precursorsTPQG-Cu-MOF active material

Solventsanhydrous N-methyl pyrrolidone (NMP)

Additivesconductive carbon black and PVDF binder

AtmosphereR2032 cells assembled in glovebox with O2 and H2O less than 0.1 ppm

Temperature85

Timeovernight drying

Substrate orientationcarbon-coated aluminium foil

Work-upSlurry spread on carbon-coated Al foil; dried at 85 C overnight; foil cut into 9 mm disks.

Scalability contextElectrode mass loading about 1.0-1.2 mg cm-2.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	TPQG-Cu-MOF	mass ratio component 6	p005 / 1695 · Experimental: The preparation of half-cell
Additive	conductive carbon black	mass ratio component 3	p005 / 1695 · Experimental: The preparation of half-cell
Additive	poly(vinylidene) fluoride (PVDF)	mass ratio component 1	p005 / 1695 · Experimental: The preparation of half-cell
Solvent	anhydrous N-methyl pyrrolidone (NMP)	Not specified	p005 / 1695 · Experimental: The preparation of half-cell
Electrolyte	LiTFSI in DOL/DME	1 mol/L; DOL:DME = 1:1 by volume	p005 / 1695 · Experimental: The preparation of half-cell

Complete recipeSource: Main

Route 7: Solvothermal

p005 / 1695 · Experimental: TPQG-Cu-MOF · Figure 1a

Metal precursorsbis(1,1,1-trifluoropentane-2,4-dionato-O,O')copper, written as (C5H4F3O2)2Cu; SI names copper(II)trifluoroacetylacetonate

Linker precursorsTPQ-8OH

Solvents1.0 mL DMF, 1.5 mL H2O, 0.5 mL MeOH; text also states DMF, MeOH and H2O (V:V:V = 2:3:1)

Atmospheresealed vial/oven; atmosphere not specified

Temperature85

Time48

Oxidant / reductantIn-situ cyclodehydrogenation of TPQ-8OH occurred during MOF synthesis; no separate oxidant reported for the MOF step.

Work-upCool to room temperature; filter; wash with H2O (10 mL x 3), DMF (10 mL x 3), and EtOH (10 mL x 3).

ActivationDried overnight in vacuum at room temperature.

Scalability contextSmall-vial batch: 6.1 mg ligand scale; isolated yield 92%.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TPQ-8OH	6.1 mg (0.01 mmol)	p005 / 1695 · Experimental: TPQG-Cu-MOF · Figure 1a
Metal Source	(C5H4F3O2)2Cu	7.4 mg (0.02 mmol)	p005 / 1695 · Experimental: TPQG-Cu-MOF · Figure 1a
Solvent	DMF	1.0 mL	p005 / 1695 · Experimental: TPQG-Cu-MOF · Figure 1a
Solvent	H2O	1.5 mL	p005 / 1695 · Experimental: TPQG-Cu-MOF · Figure 1a
Solvent	MeOH	0.5 mL	p005 / 1695 · Experimental: TPQG-Cu-MOF · Figure 1a