Synthesis · Interfacial Synthesis of Layer-Oriented 2D Conjugated Metal-Organic Framework Films toward Directional Charge Transport

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: Air Liquid Interface

SI p. 13 · Synthesis of Cu2[PcCu-O8] MOF film

Metal precursorscopper(II) acetate

Linker precursorsPcCu-OH8

SolventsChloroform/DMF (2:1 v/v), Milli-Q water subphase

AdditivesSodium acetate

AtmosphereAmbient condition / ambient atmosphere

Temperature20

Time0.5 h solvent evaporation plus 18 h polymerisation

Substrate orientationAir/water interface; edge-on layer orientation; film transferred horizontally to substrates

Work-upAs-prepared film transferred onto substrates

Scalability contextMacroscopic homogeneous film with size over cm2 reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	PcCu-OH8	1 mg dissolved in 3 ml; 200 ul used	SI p. 13 · Synthesis of Cu2[PcCu-O8] MOF film
Solvent	chloroform/DMF	3 ml · 2:1 in volume	SI p. 13 · Synthesis of Cu2[PcCu-O8] MOF film
Solvent	Milli-Q water	40 ml	SI p. 13 · Synthesis of Cu2[PcCu-O8] MOF film
Metal Source	copper(II) acetate	5 ml · 1 mg ml^-1	SI p. 13 · Synthesis of Cu2[PcCu-O8] MOF film
Additive	sodium acetate	2 ml · 1 mg ml^-1	SI p. 13 · Synthesis of Cu2[PcCu-O8] MOF film

Complete recipeSource: Both

Route 2: Air Liquid Interface

SI p. 13 · Synthesis of Cu2[PcFe-O8] MOF film

Metal precursorscopper(II) acetate

Linker precursorsPcFe-OH8

SolventsChloroform/DMF (2:1 v/v), Milli-Q water subphase

AdditivesSodium acetate

AtmosphereAmbient condition / ambient atmosphere

Temperature20

Time0.5 h solvent evaporation plus 18 h polymerisation

Substrate orientationAir/water interface; edge-on layer orientation

Work-upAs-prepared film transferred onto substrates

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	PcFe-OH8	1 mg dissolved in 3 ml; 200 ul freshly prepared solution used	SI p. 13 · Synthesis of Cu2[PcFe-O8] MOF film
Solvent	chloroform/DMF	3 ml · 2:1 in volume	SI p. 13 · Synthesis of Cu2[PcFe-O8] MOF film
Solvent	Milli-Q water	40 ml	SI p. 13 · Synthesis of Cu2[PcFe-O8] MOF film
Metal Source	copper(II) acetate	5 ml · 1 mg ml^-1	SI p. 13 · Synthesis of Cu2[PcFe-O8] MOF film
Additive	sodium acetate	2 ml · 1 mg ml^-1	SI p. 13 · Synthesis of Cu2[PcFe-O8] MOF film

Complete recipeSource: SI

Route 3: Other

SI p. 12-13 · Synthesis of PcM-OH8

Metal precursorsPcCu-OMe

Linker precursorsAs-prepared PcCu-OMe

SolventsDry dichloromethane; methanol quench; MeOH, water, dichloromethane washes

AdditivesBoron tribromide

AtmosphereArgon during BBr3 addition; dried under vacuum

Temperatureroom temperature then reflux

Time2 h room temperature; 20 h reflux

Oxidant / reductantBoron tribromide demethylation reagent

Work-upMethanol added slowly; precipitates filtered, washed with MeOH/water/dichloromethane, centrifuged until supernatant transparent, dried under vacuum

ActivationVacuum drying

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	as-prepared PcCu-OMe	2 g	SI p. 12-13 · Synthesis of PcM-OH8
Solvent	dry dichloromethane	300 ml	SI p. 12-13 · Synthesis of PcM-OH8
Other	boron tribromide	4.8 ml	SI p. 12-13 · Synthesis of PcM-OH8
Solvent	methanol	50 ml added after cooling	SI p. 12-13 · Synthesis of PcM-OH8

Complete recipeSource: SI

Route 4: Other

SI p. 12 · Synthesis of PcM-OH8

Metal precursorsCuCN

Linker precursors1,2-dibromo-4,5-dimethoxybenzene

SolventsDMF; methanol and acetone Soxhlet extraction

AdditivesConcentrated ammonium hydroxide, then diluted ammonium hydroxide wash

AtmosphereAir after ammonium hydroxide addition

Temperature165

Time5 h reflux; 12 h room-temperature stirring; 1 day Soxhlet extraction

Work-upFiltered, washed with diluted ammonium hydroxide and water; Soxhlet extracted with methanol and acetone; green solid collected

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1, 2-dibromo-4, 5-dimethoxybenzene	8.87 g, 0.03 mol	SI p. 12 · Synthesis of PcM-OH8
Metal Source	CuCN	8.06 g, 0.09 mol	SI p. 12 · Synthesis of PcM-OH8
Solvent	DMF	Not specified	SI p. 12 · Synthesis of PcM-OH8
Base	concentrated ammonium hydroxide	300 ml	SI p. 12 · Synthesis of PcM-OH8
Solvent	methanol	Soxhlet extraction for 1 day	SI p. 12 · Synthesis of PcM-OH8
Solvent	acetone	Soxhlet extraction for 1 day	SI p. 12 · Synthesis of PcM-OH8

Complete recipeSource: SI

Route 5: Solvothermal

SI p. 13 · Synthesis of PcM-OH8

Metal precursorsFe(acac)2; PcCu-OH8

Linker precursorsPcCu-OH8 precursor ligand

SolventsDMF, water

AdditivesNH3.H2O (v/v 50%)

AtmosphereStandard vacuum-line and Schlenk techniques under argon or vacuum stated generally for reagents

Temperature120

Time40

Work-upFiltered, washed with DMF, H2O, and acetone, vacuum dried at room temperature

ActivationVacuum drying

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	PcCu-OH8	0.005 mmol	SI p. 13 · Synthesis of PcM-OH8
Solvent	DMF	25 ml	SI p. 13 · Synthesis of PcM-OH8
Base	NH3.H2O	2.2 ml · v/v: 50%	SI p. 13 · Synthesis of PcM-OH8
Solvent	H2O	30 ml	SI p. 13 · Synthesis of PcM-OH8
Metal Source	Fe(acac)2 solution	5 ml, 0.01 mmol	SI p. 13 · Synthesis of PcM-OH8