Synthesis · Two-Dimensional Conjugated Metal–Organic Frameworks with a Ring-in-Ring Topology and High Electrical Conductance

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: Liquid Liquid Interface

S21 · Preparation of M-DHHBTN MOF Films · Section 10.1

Metal precursorsCo(OAc)2.4H2O

Linker precursorsDHHBTN

Solvents10 mL DHHBTN mixed solution (NMP:ethyl acetate = 1:4) and 10 mL aqueous metal-salt solution

AdditivesNone reported

AtmosphereAmbient; left undisturbed

Temperatureroom temperature

Time48

Substrate orientationMOF film formed at organic phase/water interface and transferred to quartz substrate

Oxidant / reductantNo separate oxidant/reductant specified

Work-upMOF membrane delicately transferred onto a 2 cm x 2 cm quartz substrate.

ActivationNo post-synthetic activation specified for UV-vis-NIR/OPTP films.

Scalability contextGlass garden vessel, diameter 90 mm; film prepared at liquid/liquid interface.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	DHHBTN	1.72 umol, 1.5 mg	S21 · Preparation of M-DHHBTN MOF Films · Section 10.1
Metal Source	Co(OAc)2.4H2O	6.89 umol, 1.72 mg · aqueous solution in 10 mL	S21 · Preparation of M-DHHBTN MOF Films · Section 10.1
Solvent	NMP:ethyl acetate	10 mL · 1:4	S21 · Preparation of M-DHHBTN MOF Films · Section 10.1
Solvent	water	10 mL	S21 · Preparation of M-DHHBTN MOF Films · Section 10.1

Complete recipeSource: Both

Route 2: Solvothermal

S8 · Synthesis of Co-DHHBTN MOF · Scheme S2

Metal precursorsCobalt(II) acetate tetrahydrate

Linker precursorsDHHBTN

Solvents1 mL N-methylpyrrolidone (NMP) and 3 mL H2O

AdditivesNone reported

AtmosphereGently capped in air

Temperature85

Time24

Oxidant / reductantNo separate oxidant/reductant; metal salts may participate in redox during coordination, discussed for mixed-valence products.

Work-upCollected through centrifugation, washed with water and ethanol.

ActivationDried under vacuum for 24 h at 40 C. Additional measurement-specific activation: water soaking at 60 C for 18 h and vacuum drying at 60 C for BET; ethanol/water solvent thermal activations before elemental analysis.

Scalability contextSmall-vial synthesis in 8 mL glass vial.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	DHHBTN	8.71 mg, 0.01 mmol	S8 · Synthesis of Co-DHHBTN MOF · Scheme S2
Solvent	N-methylpyrrolidone (NMP)	1 mL	S8 · Synthesis of Co-DHHBTN MOF · Scheme S2
Solvent	H2O	3 mL	S8 · Synthesis of Co-DHHBTN MOF · Scheme S2
Metal Source	Cobalt(II) acetate tetrahydrate	9.9 mg, 0.04 mmol	S8 · Synthesis of Co-DHHBTN MOF · Scheme S2

Complete recipeSource: SI

Route 3: Liquid Liquid Interface

S21 · Preparation of M-DHHBTN MOF Films · Section 10.1

Metal precursorsCu(OAc)2.H2O

Linker precursorsDHHBTN

Solvents10 mL DHHBTN mixed solution (NMP:ethyl acetate = 1:4) and 10 mL aqueous metal-salt solution

AdditivesNone reported

AtmosphereAmbient; left undisturbed

Temperatureroom temperature

Time48

Substrate orientationMOF film formed at organic phase/water interface and transferred to quartz substrate

Oxidant / reductantNo separate oxidant/reductant specified

Work-upMOF membrane delicately transferred onto a 2 cm x 2 cm quartz substrate.

ActivationNo post-synthetic activation specified for UV-vis-NIR/OPTP films.

Scalability contextGlass garden vessel, diameter 90 mm; film prepared at liquid/liquid interface.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	DHHBTN	1.72 umol, 1.5 mg	S21 · Preparation of M-DHHBTN MOF Films · Section 10.1
Metal Source	Cu(OAc)2.H2O	6.89 umol, 1.38 mg · aqueous solution in 10 mL	S21 · Preparation of M-DHHBTN MOF Films · Section 10.1
Solvent	NMP:ethyl acetate	10 mL · 1:4	S21 · Preparation of M-DHHBTN MOF Films · Section 10.1
Solvent	water	10 mL	S21 · Preparation of M-DHHBTN MOF Films · Section 10.1

Complete recipeSource: Both

Route 4: Solvothermal

S9 · Synthesis of Cu-DHHBTN MOF · Scheme S4

Metal precursorsCopper(II) trifluoroacetylacetonate

Linker precursorsDHHBTN

Solvents1 mL N-methylpyrrolidone (NMP) and 3 mL H2O

AdditivesNone reported

AtmosphereGently capped in air

Temperature85

Time24

Oxidant / reductantNo separate oxidant/reductant; metal salts may participate in redox during coordination, discussed for mixed-valence products.

Work-upCollected through centrifugation, washed with water and ethanol.

Scalability contextSmall-vial synthesis in 8 mL glass vial.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	DHHBTN	17.42 mg, 0.02 mmol	S9 · Synthesis of Cu-DHHBTN MOF · Scheme S4
Solvent	N-methylpyrrolidone (NMP)	1 mL	S9 · Synthesis of Cu-DHHBTN MOF · Scheme S4
Solvent	H2O	3 mL	S9 · Synthesis of Cu-DHHBTN MOF · Scheme S4
Metal Source	Copper(II) trifluoroacetylacetonate	29.6 mg, 0.08 mmol	S9 · Synthesis of Cu-DHHBTN MOF · Scheme S4

Complete recipeSource: SI

Route 5: Other

S4-S5 · Synthesis of DHHBTN · Scheme S1

Metal precursorsNone

Linker precursorsTriphenylene-derived brominated and hexyloxy intermediates

Solventsnitrobenzene; dichlorobenzene; toluene/ethanol/water; dichloromethane; methanol; petroleum ether eluent

Additivesiron shavings; Pd(PPh3)4; K2CO3; FeCl3; BBr3

AtmosphereN2 for final BBr3 dealkylation; other steps not fully specified

Temperature205 reflux; 120; room temperature; 0 to 45

Time16 + 2; 16; 3; 4 h plus 7 d

Oxidant / reductantBr2 bromination; FeCl3 Scholl oxidation; BBr3 dealkylation

Work-upfiltration, ether rinsing, recrystallisation/chilling, column chromatography, methanol quench/wash, water quench and filtration

ActivationDHHBTN was dried/used after synthesis; ATR-IR sample further dried in vacuum desiccator with oil pump for 24 h at room temperature.

Scalability contextMulti-step ligand synthesis; final DHHBTN reported 161 mg, 70% yield.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	triphenylene	4.95 mmol, 1.13 g	S4-S5 · Synthesis of DHHBTN · Scheme S1
Oxidant	liquid bromine	42.6 mmol, 2.2 mL	S4-S5 · Synthesis of DHHBTN · Scheme S1
Additive	iron shavings	1.78 mmol, 100 mg	S4-S5 · Synthesis of DHHBTN · Scheme S1
Additive	Pd(PPh3)4	0.501 g, 0.433 mmol	S4-S5 · Synthesis of DHHBTN · Scheme S1
Base	K2CO3	1.68 g, 12.2 mmol · aqueous solution in 7 mL	S4-S5 · Synthesis of DHHBTN · Scheme S1
Oxidant	FeCl3	2.73 g, 16.85 mmol	S4-S5 · Synthesis of DHHBTN · Scheme S1
Other	BBr3	9.58 mmol, 0.93 mL	S4-S5 · Synthesis of DHHBTN · Scheme S1

Complete recipeSource: SI

Route 6: Liquid Liquid Interface

S21 · Preparation of M-DHHBTN MOF Films · Section 10.1

Metal precursorsNi(OAc)2.4H2O

Linker precursorsDHHBTN

Solvents10 mL DHHBTN mixed solution (NMP:ethyl acetate = 1:4) and 10 mL aqueous metal-salt solution

AdditivesNone reported

AtmosphereAmbient; left undisturbed

Temperatureroom temperature

Time48

Substrate orientationMOF film formed at organic phase/water interface and transferred to quartz substrate

Oxidant / reductantNo separate oxidant/reductant specified

Work-upMOF membrane delicately transferred onto a 2 cm x 2 cm quartz substrate.

ActivationNo post-synthetic activation specified for UV-vis-NIR/OPTP films.

Scalability contextGlass garden vessel, diameter 90 mm; film prepared at liquid/liquid interface.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	DHHBTN	1.72 umol, 1.5 mg	S21 · Preparation of M-DHHBTN MOF Films · Section 10.1
Metal Source	Ni(OAc)2.4H2O	6.89 umol, 1.71 mg · aqueous solution in 10 mL	S21 · Preparation of M-DHHBTN MOF Films · Section 10.1
Solvent	NMP:ethyl acetate	10 mL · 1:4	S21 · Preparation of M-DHHBTN MOF Films · Section 10.1
Solvent	water	10 mL	S21 · Preparation of M-DHHBTN MOF Films · Section 10.1

Complete recipeSource: Both

Route 7: Solvothermal

S9 · Synthesis of Ni-DHHBTN MOF · Scheme S3

Metal precursorsNickel(II) acetate tetrahydrate

Linker precursorsDHHBTN

Solvents1 mL N-methylpyrrolidone (NMP) and 3 mL H2O

AdditivesNone reported

AtmosphereGently capped in air

Temperature85

Time24

Oxidant / reductantNo separate oxidant/reductant; metal salts may participate in redox during coordination, discussed for mixed-valence products.

Work-upCollected through centrifugation, washed with water and ethanol.

Scalability contextSmall-vial synthesis in 8 mL glass vial.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	DHHBTN	17.42 mg, 0.02 mmol	S9 · Synthesis of Ni-DHHBTN MOF · Scheme S3
Solvent	N-methylpyrrolidone (NMP)	1 mL	S9 · Synthesis of Ni-DHHBTN MOF · Scheme S3
Solvent	H2O	3 mL	S9 · Synthesis of Ni-DHHBTN MOF · Scheme S3
Metal Source	Nickel(II) acetate tetrahydrate	19.9 mg, 0.08 mmol	S9 · Synthesis of Ni-DHHBTN MOF · Scheme S3