Synthesis · Triazacoronene-Based 2D Conductive Metal–Organic Framework for High-Capacity Lithium Storage

Complete recipeSource: SI

Route 1: Drop Cast

SI p.2 · Electrochemical Measurements

Solventsdeionized water

AdditivesKetjen Black conductive additive; carboxymethyl cellulose (CMC) binder

Atmospherevacuum drying; Ar-filled glovebox for coin-cell assembly

Temperature80

Time12

Substrate orientationCu foil current collector

Work-upSlurry ground for 30 min, uniformly coated onto Cu foil, dried, punched into 1.2 cm discs.

ActivationVacuum oven drying at 80 degC for 12 h.

Scalability contextActive material areal loading focused on 0.8-1.0 mg cm^-2.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-TAC electroactive material	70 wt% of electrode solids	SI p.2 · Electrochemical Measurements
Additive	Ketjen Black	20 wt% of electrode solids	SI p.2 · Electrochemical Measurements
Additive	carboxymethyl cellulose (CMC)	10 wt% of electrode solids	SI p.2 · Electrochemical Measurements
Solvent	deionized water	not specified	SI p.2 · Electrochemical Measurements
Electrolyte	LiPF6 in EC/DEC/DMC	not specified · 1 M; 1:1:1 volume ratio	SI p.2 · Electrochemical Measurements

Complete recipeSource: Both

Route 2: Solvothermal

SI p.8 · Synthesis of Cu-TAC

Metal precursorsCu(NO3)2.3H2O

Linker precursors6OH-TAC monomer

SolventsN-methyl-2-pyrrolidone (NMP) and H2O

Additivesethylenediamine aqueous solution (10%, ca.) and ammonia (25%, ca.)

Atmospheresealed vial; atmosphere not otherwise specified

Temperature80

Time48

Work-upUltrasonication 20 min before heating; after cooling, powder collected and washed successively with DMF, deionized water and ethanol several times.

ActivationDried under vacuum overnight.

Scalability contextSmall-scale synthesis: 6.0 mg Cu-TAC, 98% yield based on 6OH-TAC.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	6OH-TAC monomer	5.0 mg, 0.0125 mmol	SI p.8 · Synthesis of Cu-TAC
Metal Source	Cu(NO3)2.3H2O	4.7 mg, 0.0195 mmol	SI p.8 · Synthesis of Cu-TAC
Solvent	N-methyl-2-pyrrolidone (NMP)	0.5 mL	SI p.8 · Synthesis of Cu-TAC
Solvent	H2O	2.0 mL	SI p.8 · Synthesis of Cu-TAC
Base	ethylenediamine aqueous solution	300 uL · 10%, ca.	SI p.8 · Synthesis of Cu-TAC
Base	ammonia	30 uL · 25%, ca.	SI p.8 · Synthesis of Cu-TAC

Complete recipeSource: SI

Route 3: Drop Cast

SI p.2 · Electrochemical Measurements

Solventsdeionized water

AdditivesKetjen Black conductive additive; carboxymethyl cellulose (CMC) binder

Atmospherevacuum drying; Ar-filled glovebox for coin-cell assembly

Temperature80

Time12

Substrate orientationCu foil current collector

Work-upSlurry ground for 30 min, uniformly coated onto Cu foil, dried, punched into 1.2 cm discs.

ActivationVacuum oven drying at 80 degC for 12 h.

Scalability contextActive material areal loading focused on 0.8-1.0 mg cm^-2.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	6OH-TAC electroactive material	70 wt% of electrode solids	SI p.2 · Electrochemical Measurements
Additive	Ketjen Black	20 wt% of electrode solids	SI p.2 · Electrochemical Measurements
Additive	carboxymethyl cellulose (CMC)	10 wt% of electrode solids	SI p.2 · Electrochemical Measurements
Solvent	deionized water	not specified	SI p.2 · Electrochemical Measurements
Electrolyte	LiPF6 in EC/DEC/DMC	not specified · 1 M; 1:1:1 volume ratio	SI p.2 · Electrochemical Measurements

Complete recipeSource: Both

Route 4: Other

SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7

Linker precursors1,2-dimethoxybenzene; 2,3,6,7,10,11-hexamethoxytriphenylene intermediates; 3,4,7,8,11,12-hexamethoxybenzo[lmn]phenanthridino[2,1,10,9-defgh][2,8]phenanthroline (5)

Solventsdichloromethane, methanol, acetic acid, diethyl ether, tetrahydrofuran, N,N-dimethylformamide, water, ether, brine as used across steps

Additivesconcentrated sulfuric acid, fuming nitric acid, Ni(OAc)2.4H2O, paraformaldehyde, trifluoromethanesulfonic acid, 1 M NaOH, pyridine hydrochloride

Atmospherenot specified

Temperature0 degC to room temperature; reflux; 120 degC drying; 100 degC cyclization; 200 degC demethylation

Time4 h trimerization; 12 h nitration reflux; 24 h reduction; 24 h cyclization; 4 h demethylation

Oxidant / reductantFeCl3/H2SO4 oxidative trimerization; fuming HNO3 nitration; NaBH4/Ni(OAc)2 reduction

Work-upFiltration, washing, drying, silica-gel chromatography, extraction, recrystallization and centrifugation as step-specific workups.

ActivationFinal 6OH-TAC dried at 120 degC for 12 h.

Scalability contextFinal 6OH-TAC isolated as 0.36 g, 90% yield; overall route uses multistep organic synthesis.

Show 20 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1,2-dimethoxybenzene	13.8 mL, 108.6 mmol	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Oxidant	anhydrous ferric chloride	52.8 g, 325.8 mmol	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Acid	concentrated sulfuric acid	0.75 mL	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Solvent	dichloromethane	200 mL plus 75 mL in first step; 70 mL in nitration step	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Other	2,3,6,7,10,11-hexamethoxytriphenylene (2)	13.8 g, 25.4 mmol for nitration	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Acid	fuming nitric acid	21 mL	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Solvent	acetic acid	70 mL	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Solvent	diethyl ether	70 mL	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Other	2,3,6,7,10,11-hexamethoxy-1,5,9-trinitrotriphenylene (3)	5.4 g, 11.9 mmol	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Reductant	sodium borohydride	5.6 g, 148.0 mmol	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Additive	Ni(OAC)2.4H2O	2.5 g, 10.0 mmol	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Solvent	tetrahydrofuran	180 mL	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Solvent	methanol	45 mL reduction step; 200 mL quench first step	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Other	2,3,6,7,10,11-hexamethoxytriphenylene-1,5,9-triamine (4)	4.2 g, 8.7 mmol	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Additive	paraformaldehyde	5.0 g, 55.6 mmol	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Solvent	N,N-dimethylformamide	50 mL	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Acid	trifluoromethanesulfonic acid	500 uL	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Other	compound 5	0.48 g, 0.99 mmol	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Acid	pyridine hydrochloride	25 g, 216 mmol	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7
Solvent	deionized water	100 mL in final 6OH-TAC workup	SI p.3-8 · Synthesis and Characterization · Scheme S1, Figures S1-S7

Triazacoronene-Based 2D Conductive Metal–Organic Framework for High-Capacity Lithium Storage

4 structured synthesis routes