Synthesis · Stabilizing Redox-Active Hexaazatriphenylene in a 2D Conductive Metal–Organic Framework for Improved Lithium Storage Performance

6 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

3 · Electrochemical Measurements

Linker precursors6OH-HATN electroactive material

SolventsH2O

AdditivesKetjen Black conductive additive; carboxymethyl cellulose binder

Atmospherecoin cells assembled in highly pure argon glove box with water and oxygen below 0.1 ppm

Temperature80

Time12

Substrate orientationcopper foil

Work-upGround 30 min to form slurry, cast onto copper foil, dried in vacuum oven, cut into 1.2 cm discs.

ActivationElectrochemical cycling.

Scalability contextAreal active-material loading 0.7-1.0 mg cm^-2.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	6OH-HATN	7 parts by weight	3 · Electrochemical Measurements
Additive	Ketjen Black	2 parts by weight	3 · Electrochemical Measurements
Additive	carboxymethyl cellulose (CMC)	1 part by weight	3 · Electrochemical Measurements

Complete recipeSource: SI

Route 2: Other

4-7 · Synthesis and Characterization · Scheme S1

Linker precursors1,2-dimethoxybenzene; 1,2-dimethoxy-4,5-dinitrobenzene; 4,5-dimethoxybenzene-1,2-diamine; hexaketocyclohexane octahydrate; 2,3,8,9,14,15-hexamethoxydiquinoxalino[2,3-a:2',3'-c]phenazine

Solventsnitric acid; ethanol; acetic acid; water

AdditivesPd/C; hydrazine hydrate; pyridine hydrochloride

AtmosphereAr for diamine and hexamethoxy intermediate steps; not specified for final pyridine hydrochloride deprotection

Temperature80; 80; 120; 200

Time2; 2; 12; 4

Oxidant / reductant65% concentrated nitric acid; hydrazine hydrate/Pd-C

Work-upFiltration, washing with deionized water/hot acetic acid/acetone/ethanol/water as applicable; centrifugation for final black precipitate; washed to neutral.

ActivationFinal 6OH-HATN dried at 120 deg C for 12 h.

Scalability contextBatch masses reported for all steps; final 6OH-HATN yield 0.41 g, 96%.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1,2-dimethoxybenzene	10 mL, 78.2 mmol	4-7 · Synthesis and Characterization · Scheme S1
Acid	65% concentrated nitric acid	100 mL · 65%	4-7 · Synthesis and Characterization · Scheme S1
Reductant	hydrazine hydrate	6 mL, 123.4 mmol	4-7 · Synthesis and Characterization · Scheme S1
Additive	Pd/C	1.15 g, 10.8 mmol	4-7 · Synthesis and Characterization · Scheme S1
Linker	hexaketocyclohexane octahydrate	0.93 g, 2.98 mmol	4-7 · Synthesis and Characterization · Scheme S1
Acid	acetic acid	125 mL	4-7 · Synthesis and Characterization · Scheme S1
Additive	pyridine hydrochloride	20 g, 173 mmol	4-7 · Synthesis and Characterization · Scheme S1

Complete recipeSource: SI

Route 3: Drop Cast

3 · Electrochemical Measurements

Linker precursorsCu-HATN electroactive material

SolventsH2O

AdditivesKetjen Black conductive additive; carboxymethyl cellulose binder

Atmospherecoin cells assembled in highly pure argon glove box with water and oxygen below 0.1 ppm

Temperature80

Time12

Substrate orientationcopper foil

Work-upGround 30 min to form slurry, cast onto copper foil, dried in vacuum oven, cut into 1.2 cm discs.

Activation50 cycles activation at 150 mA g^-1 before main rate test; electrochemical cycling activates MOF.

Scalability contextAreal active-material loading 0.7-1.0 mg cm^-2.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-HATN	7 parts by weight	3 · Electrochemical Measurements
Additive	Ketjen Black	2 parts by weight	3 · Electrochemical Measurements
Additive	carboxymethyl cellulose (CMC)	1 part by weight	3 · Electrochemical Measurements
Solvent	H2O	Not specified	3 · Electrochemical Measurements

Complete recipeSource: Both

Route 4: Hydrothermal

9-10 · Synthesis of Cu-HATN · Scheme S2

Metal precursorsCu(NO3)2.6H2O

Linker precursors6OH-HATN

Solventsdeionized water

Additivesethylenediamine aqueous solution; ammonia water

Atmospheresealed vial; atmosphere not otherwise specified

Temperature85

Time48

Work-upNaturally cooled to room temperature; black powders collected and washed with DMF, deionized water, and ethanol several times.

ActivationDried at 120 deg C overnight.

Scalability contextSI reports 5 mg ligand recipe and final product yield 5.6 g, 95% based on 6OH-HATN; mass appears internally inconsistent and is flagged in audit.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	6OH-HATN	5 mg, 0.0104 mmol	9-10 · Synthesis of Cu-HATN · Scheme S2
Metal Source	Cu(NO3)2.6H2O	4.7 mg, 0.0158 mmol	9-10 · Synthesis of Cu-HATN · Scheme S2
Solvent	deionized water	2.5 mL	9-10 · Synthesis of Cu-HATN · Scheme S2
Base	ethylenediamine aqueous solution	300 uL · 10%, ca.	9-10 · Synthesis of Cu-HATN · Scheme S2
Base	ammonia water	75 uL · 25%, ca.	9-10 · Synthesis of Cu-HATN · Scheme S2

Complete recipeSource: SI

Route 5: Drop Cast

3 · Electrochemical Measurements

Linker precursorsHATN electroactive material

SolventsH2O

AdditivesKetjen Black conductive additive; carboxymethyl cellulose binder

Atmospherecoin cells assembled in highly pure argon glove box with water and oxygen below 0.1 ppm

Temperature80

Time12

Substrate orientationcopper foil

Work-upGround 30 min to form slurry, cast onto copper foil, dried in vacuum oven, cut into 1.2 cm discs.

ActivationElectrochemical cycling; HATN capacity decreases strongly because of solubility.

Scalability contextAreal active-material loading 0.7-1.0 mg cm^-2.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	HATN	7 parts by weight	3 · Electrochemical Measurements
Additive	Ketjen Black	2 parts by weight	3 · Electrochemical Measurements
Additive	carboxymethyl cellulose (CMC)	1 part by weight	3 · Electrochemical Measurements

Complete recipeSource: SI

Route 6: Other

8 · Synthesis of hexaazatrinaphthalene (HATN) · Figures S7-S8

Linker precursorsbenzene-1,2-diamine; hexaketocyclohexane octahydrate

Solventsacetic acid

AtmosphereAr

Temperature120

Time12

Work-upFiltered, rinsed with hot acetic acid, acetone, ethanol, and water successively.

ActivationDried in oven; pale green powders obtained.

Scalability contextYield 0.9 g, 92%.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	benzene-1,2-diamine	1.0 g, 9.2 mmol	8 · Synthesis of hexaazatrinaphthalene (HATN) · Figures S7-S8
Linker	hexaketocyclohexane octahydrate	0.8 g, 2.56 mmol	8 · Synthesis of hexaazatrinaphthalene (HATN) · Figures S7-S8
Solvent	acetic acid	100 mL	8 · Synthesis of hexaazatrinaphthalene (HATN) · Figures S7-S8