Synthesis · Two-dimensional d-π conjugated metal-organic framework based on hexahydroxytrinaphthylene

4 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Solvothermal

6 · S2.2 Synthesis of Cu3(HHTN)2 MOF · Table S1

Metal precursorscopper(II) acetate

Linker precursorsHHTN

SolventsDMI/H2O (v/v=3:1), 15 mL

Additivesconcentrated ammonia water (25%-28%, 150 eq to HHTN)

Atmosphereair; vial loosely capped

Temperature65

Time24

Work-upFiltered; washed with water (5 x 20 mL) and acetone (5 x 20 mL); oil-pump dried at room temperature for 1 day.

ActivationAs-synthesised sample used directly for PXRD, FTIR, XPS, UV-vis-NIR, and elemental analysis; separate sorption activation used acetone exchange/supercritical CO2/vacuum degassing.

Scalability context20 mL vial scale; 75 mg product, 87% yield based on Cu3(HHTN)2 formula.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper(II) acetate	54.5 mg, 0.30 mmol, 2 eq. to HHTN	6 · S2.2 Synthesis of Cu3(HHTN)2 MOF · Table S1
Solvent	DMI/H2O	15 mL · v/v=3:1	6 · S2.2 Synthesis of Cu3(HHTN)2 MOF · Table S1
Base	concentrated ammonia water	1.50 mL, 150 eq to HHTN · 25%-28%	6 · S2.2 Synthesis of Cu3(HHTN)2 MOF · Table S1
Linker	HHTN	71 mg, 0.15 mmol	6 · S2.2 Synthesis of Cu3(HHTN)2 MOF · Table S1

Partial recipeSource: SI

Route 2: Solvothermal

6 · S2.2 Synthesis of Cu3(HHTN)2 MOF · Table S1

Metal precursorsCu source varied; Cu(NO3)2 used in entries 15 and 16; optimised entry uses copper(II) acetate

Linker precursorsHHTN

SolventsDMSO, H2O, DMSO:H2O, benzene:DMSO, H2O:DMI, H2O:NMP

AdditivesNH3·H2O, NH4OAc, ethylenediamine, Cu(NO3)2

AtmosphereN2 for Table S1 entry 1; otherwise not specified or air in optimised recipe

Temperature65-150

Time24-72

Work-upScreening workup not individually detailed; optimised route filtered/washed/dried.

Scalability context16-condition screen; highly crystalline material from entries 7, 9, 14, 15 and 16.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTN	[L] = 5, 10, or 30 mM	6 · S2.2 Synthesis of Cu3(HHTN)2 MOF · Table S1
Base	NH3·H2O	50, 150, or 300 eq in Table S1	6 · S2.2 Synthesis of Cu3(HHTN)2 MOF · Table S1
Base	ethylenediamine (en)	50 eq in Table S1	6 · S2.2 Synthesis of Cu3(HHTN)2 MOF · Table S1

Complete recipeSource: SI

Route 3: Other

2-4 · S2.1 Synthesis of HHTN Ligand · Schemes S1-S2

Metal precursorsNi(1,5-COD)2 used in Yamamoto-type coupling for HMTN precursor; no MOF metal node in this ligand synthesis

Linker precursors2,3-dihydroxynaphthalene via tetrabromodiol, dibromodiol, dimethoxy dibromonaphthalene 4, HMTN, then HHTN

Solventsglacial acetic acid, acetonitrile, dry THF, dichloromethane, water

AdditivesBr2, SnCl2·2H2O, concentrated HCl, K2CO3, iodomethane, 1,5-cyclooctadiene, 2,2'-bipyridine, BBr3

AtmosphereAr for HMTN coupling; dry DCM/ice bath for demethylation

Temperaturereflux for bromination/reduction; 75 °C for methylation; ambient for HMTN coupling; r.t. for 24 h BBr3 demethylation

Time1 h bromination reflux; 50 min reduction reflux; 18 h methylation; 18 h HMTN coupling after addition; 24 h demethylation

Oxidant / reductantBr2 bromination; SnCl2/HCl reduction/debromination; BBr3 demethylation

Work-upFiltration/washing/drying at each step; DCM extraction/washing; freezer crystallisation; column chromatography for mother liquor; HHTN filtered, washed with water, dried under vacuum.

Scalability contextReported isolated yields: compound 2 94%, compound 3 77%, compound 4 92%, HMTN 42%, HHTN 89%.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	2,3-Dihydroxynaphthalene	9.0 g, 56 mmol	2-4 · S2.1 Synthesis of HHTN Ligand · Schemes S1-S2
Oxidant	liquid bromine	12.8 mL	2-4 · S2.1 Synthesis of HHTN Ligand · Schemes S1-S2
Reductant	tin(II) chloride dihydrate	80 g	2-4 · S2.1 Synthesis of HHTN Ligand · Schemes S1-S2
Base	K2CO3	10.9 g, 78.5 mmol, 2.5 equivalents	2-4 · S2.1 Synthesis of HHTN Ligand · Schemes S1-S2
Additive	iodomethane	4.9 mL, 78.5 mmol, 2.5 equivalents	2-4 · S2.1 Synthesis of HHTN Ligand · Schemes S1-S2
Additive	Ni(1,5-COD)2	2.1 g, 7.5 mmol, 1.25 equiv	2-4 · S2.1 Synthesis of HHTN Ligand · Schemes S1-S2
Additive	boron tribromide	1.3 mL, 13 mmol, 18 equivalents	2-4 · S2.1 Synthesis of HHTN Ligand · Schemes S1-S2

Complete recipeSource: SI

Route 4: Other

16 · S11 I2 Doping Study of Cu3(HHTN)2 · Fig. S28

Metal precursorspreformed Cu3(HHTN)2 from entry 9

Linker precursorspreformed Cu3(HHTN)2 framework

Solventsacetone for washing

AdditivesI2

Atmospheresealed glass vial during iodine treatment

Temperature40

Time12

Oxidant / reductantI2 oxidative dopant

Work-upRepeated immersion in acetone and decanting until solution became colourless; oil-pump vacuum drying at room temperature for 1 day.

Scalability context30 mg MOF treated with 15 mg I2.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3(HHTN)2 obtained from entry 9	30 mg	16 · S11 I2 Doping Study of Cu3(HHTN)2 · Fig. S28
Oxidant	I2	15 mg	16 · S11 I2 Doping Study of Cu3(HHTN)2 · Fig. S28
Solvent	acetone	Not specified	16 · S11 I2 Doping Study of Cu3(HHTN)2 · Fig. S28