Synthesis · Synthesis of a copper 1,3,5-triamino-2,4,6-benzenetriol metal-organic framework

5 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Hydrothermal

S3 · Synthesis of Cu3(TABTO)2

Metal precursorsCu(NO3)2.3H2O (112.2 mg, 0.6 mmol)

Linker precursorsTABTO (55.8 mg, 0.2 mmol)

SolventsDegassed H2O, 15 mL plus 15 mL

AdditivesEthylenediamine (73 uL, 1.1 mmol)

AtmosphereAir with vigorous stirring

Temperature80 in SI; main text states 85 C

Time48

Oxidant / reductantOxygen exposure during stirring prevents Cu metal formation; ligand can reduce Cu(II).

Work-upFiltered and washed with THF, water, and methanol.

ActivationDried under high vacuum (10-3 torr) for 8 h.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.3H2O	112.2 mg, 0.6 mmol	S3 · Synthesis of Cu3(TABTO)2
Linker	1,3,5-triamino-2,4,6-benzenetriol (TABTO)	55.8 mg, 0.2 mmol	S3 · Synthesis of Cu3(TABTO)2
Base	ethylenediamine	73 uL, 1.1 mmol	S3 · Synthesis of Cu3(TABTO)2
Solvent	degassed H2O	30 mL total	S3 · Synthesis of Cu3(TABTO)2

Complete recipeSource: Both

Route 2: Air Liquid Interface

S3 · Synthesis of Cu3(TABTO)2

Metal precursorsCu(NO3)2.3H2O (112.2 mg, 0.6 mmol)

Linker precursorsTABTO (55.8 mg, 0.2 mmol)

SolventsDegassed H2O, 15 mL plus 15 mL

AdditivesEthylenediamine (73 uL, 1.1 mmol)

AtmosphereAir without stirring

Temperature80

Time48

Substrate orientationAir/water interface MOF film forms without stirring

Oxidant / reductantRestricted oxygen entry allows copper metal formation.

Work-upFiltered and washed with THF, water, and methanol.

ActivationDried under high vacuum (10-3 torr) for 8 h.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.3H2O	112.2 mg, 0.6 mmol	S3 · Synthesis of Cu3(TABTO)2
Linker	1,3,5-triamino-2,4,6-benzenetriol (TABTO)	55.8 mg, 0.2 mmol	S3 · Synthesis of Cu3(TABTO)2
Base	ethylenediamine	73 uL, 1.1 mmol	S3 · Synthesis of Cu3(TABTO)2
Solvent	degassed H2O	30 mL total	S3 · Synthesis of Cu3(TABTO)2

Complete recipeSource: Both

Route 3: Hydrothermal

S3 · Synthesis of Cu3(TABTO)2

Metal precursorsCu(NO3)2.3H2O (112.2 mg, 0.6 mmol)

Linker precursors1,3,5-triamino-2,4,6-benzenetriol (TABTO, 55.8 mg, 0.2 mmol)

SolventsDegassed H2O, 15 mL for copper solution plus 15 mL for linker solution

AdditivesEthylenediamine (73 uL, 1.1 mmol)

AtmosphereAr

Temperature80

Time48

Oxidant / reductantLigand partially reduces Cu(II); no external oxidant.

Work-upSolid collected by filtration and washed with THF, water, and methanol.

ActivationDried under high vacuum (10-3 torr) for 8 h.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.3H2O	112.2 mg, 0.6 mmol	S3 · Synthesis of Cu3(TABTO)2
Linker	1,3,5-triamino-2,4,6-benzenetriol (TABTO)	55.8 mg, 0.2 mmol	S3 · Synthesis of Cu3(TABTO)2
Base	ethylenediamine	73 uL, 1.1 mmol	S3 · Synthesis of Cu3(TABTO)2
Solvent	degassed H2O	30 mL total	S3 · Synthesis of Cu3(TABTO)2

Complete recipeSource: Both

Route 4: Other

S3-S4 · Synthesis of iodine-doped Cu3(TABTO)2-Ar and -Air-1

Metal precursorsCu3(TABTO)2-Air-1 powder (100.0 mg, 0.19 mmol based on theoretical Cu3(TABTO)2)

Linker precursorsFramework already formed

Solventsn-Hexane wash after doping

AdditivesIodine (2.0 g, 7.9 mmol)

AtmosphereSealed iodine vapour treatment

Temperature65

Time8

Oxidant / reductantIodine dopant/oxidant.

Work-upWashed with n-hexane.

ActivationDried under vacuum (10-3 Torr) for 8 h.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Oxidant	iodine	2.0 g, 7.9 mmol	S3-S4 · Synthesis of iodine-doped Cu3(TABTO)2-Ar and -Air-1
Other	Cu3(TABTO)2-Air-1 powder	100.0 mg, 0.19 mmol	S3-S4 · Synthesis of iodine-doped Cu3(TABTO)2-Ar and -Air-1
Solvent	n-hexane	separate amounts for washing	S3-S4 · Synthesis of iodine-doped Cu3(TABTO)2-Ar and -Air-1

Complete recipeSource: Both

Route 5: Other

S3-S4 · Synthesis of iodine-doped Cu3(TABTO)2-Ar and -Air-1

Metal precursorsPristine Cu3(TABTO)2-Ar powder (100 mg nominal; SI line contains likely 'Air' typo)

Linker precursorsFramework already formed

Solventsn-Hexane wash after doping

AdditivesIodine (2.0 g, 7.9 mmol) in larger sealed container

AtmosphereSealed iodine vapour treatment

Temperature65

Time8

Oxidant / reductantIodine oxidant/dopant; produces I3- and CuI, converts Cu(II) to Cu(I).

Work-upWashed with separate amounts of n-hexane to remove unreacted iodine.

ActivationDried under vacuum (10-3 Torr) for 8 h.

Scalability contextDoping performed on 100 mg powder in a 5.0 mL inner container inside a 15.0 mL iodine container.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Oxidant	iodine	2.0 g, 7.9 mmol	S3-S4 · Synthesis of iodine-doped Cu3(TABTO)2-Ar and -Air-1
Other	pristine Cu3(TABTO)2-Ar powder	100 mg	S3-S4 · Synthesis of iodine-doped Cu3(TABTO)2-Ar and -Air-1
Solvent	n-hexane	separate amounts for washing	S3-S4 · Synthesis of iodine-doped Cu3(TABTO)2-Ar and -Air-1