Synthesis · Ammonia-Assisted Chemical Vapor Deposition Growth of Two-Dimensional Conjugated Coordination Polymer Thin Films

11 structured synthesis routes

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

Vague recipeSource: SI

Route 1: Cvd

SI p32 · Figure S26 discussion · Figure S26

Metal precursorsCu source, likely Cu(acac)2 by Figure 2b scheme

Linker precursorsBHT powder

Solventsnone for CVD

Additivesno NH3

AtmosphereCVD without NH3

Temperaturenot reported in the assigned documents

Timenot reported in the assigned documents

Substrate orientationSiO2/Si

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu source / Cu(acac)2 indicated in reaction scheme	Not specified	SI p32 · Figure S26 discussion · Figure S26
Linker	BHT powder	Not specified	SI p32 · Figure S26 discussion · Figure S26

Vague recipeSource: Both

Route 2: Cvd

SI p2 and p31 · CVD growth; Figure S25 · Figures 2b, S25

Metal precursorsCu source, likely Cu(acac)2 by Figure 2b scheme; exact route follows previous work

Linker precursorsBHT powder

Solventsnone for CVD

AdditivesNH3 vapour used in this strategy

AtmosphereNH3-assisted CVD

Temperaturenot reported in the assigned documents

Timenot reported in the assigned documents

Substrate orientationSiO2/Si; direct deposition also stated for quartz and flexible polymer substrates

Scalability contextDirect deposition on diverse substrates eliminates transfer-related issues.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu source / Cu(acac)2 indicated in reaction scheme	Not specified	SI p2 and p31 · CVD growth; Figure S25 · Figures 2b, S25
Linker	BHT powder	Not specified	SI p2 and p31 · CVD growth; Figure S25 · Figures 2b, S25
Base	NH3.H2O solution	Not specified	SI p2 and p31 · CVD growth; Figure S25 · Figures 2b, S25

Partial recipeSource: SI

Route 3: Cvd

SI p30 · Figure S24 discussion · Figure S24

Metal precursorsCu(acac)2 powders

Linker precursorsHHB powders

Solventsnone for CVD

Additivesno NH3

Atmospherelow-pressure CVD without NH3

TemperatureCu(acac)2 heated at 120 in Cu-HHB route; no-NH3 control not separately specified

Substrate orientationSiO2/Si substrate

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(acac)2 powders	Not specified	SI p30 · Figure S24 discussion · Figure S24
Linker	HHB powders	Not specified	SI p30 · Figure S24 discussion · Figure S24

Partial recipeSource: Both

Route 4: Cvd

SI p2 · CVD growth of 2D c-CPs thin films · Figure S23

Metal precursorsCu(acac)2 powders, copper(II) acetylacetonate

Linker precursorsHHB powders

Solventsnone for CVD

AdditivesNH3 vapour from NH3.H2O solution

AtmosphereNH3-assisted low-pressure CVD

TemperatureHHB zone 200 inferred from Fe-HHB route; Cu(acac)2 heated at 120

Timenot separately stated

Substrate orientationSiO2/Si substrate

Work-upnot separately stated

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(acac)2 powders (copper(II) acetylacetonate, Sigma-Aldrich Chemie GmbH)	Not specified	SI p2 · CVD growth of 2D c-CPs thin films · Figure S23
Linker	HHB powders	Not specified	SI p2 · CVD growth of 2D c-CPs thin films · Figure S23
Base	NH3.H2O solution	Not specified	SI p2 · CVD growth of 2D c-CPs thin films · Figure S23

Partial recipeSource: SI

Route 5: Cvd

SI p2 and p25 · Preparation of NH3.H2O solution; Figure S19 · Figure S19

Metal precursorsFe(acac)3 powders

Linker precursorsHHB powders

Solventsnone for CVD

AdditivesNH3.H2O solution concentration varied from 1.4 mmol/L to 14 mol/L; includes 0 NH3 control

AtmosphereNH3-assisted low-pressure CVD with variable NH3 vapour pressure

TemperatureHHB zone 200; Fe(acac)3 zone 105 for standard Fe-HHB programme

Substrate orientationface-to-face inner tube system

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Base	NH3.H2O solutions	1.4 mmol/L to 14 mol/L	SI p2 and p25 · Preparation of NH3.H2O solution; Figure S19 · Figure S19
Linker	HHB powders	2 mg in standard Fe-HHB route	SI p2 and p25 · Preparation of NH3.H2O solution; Figure S19 · Figure S19
Metal Source	Fe(acac)3 powders	20 mg in standard Fe-HHB route	SI p2 and p25 · Preparation of NH3.H2O solution; Figure S19 · Figure S19

Partial recipeSource: Both

Route 6: Cvd

18191 · Introduction / Results and Discussion · Figure 1

Metal precursorsFe(acac)3 powders

Linker precursorsHHB powders

Solventsnone for CVD

Additivesno NH3

AtmosphereN2 / low pressure CVD inferred from Fe-HHB route; NH3 absent

Temperaturenot separately stated; likely same Fe-HHB CVD temperature programme

Timenot separately stated

Substrate orientationSiO2/Si or quartz substrates

Work-upnot separately stated

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHB powders	Not specified	18191 · Introduction / Results and Discussion · Figure 1
Metal Source	Fe(acac)3 powders	Not specified	18191 · Introduction / Results and Discussion · Figure 1

Partial recipeSource: SI

Route 7: Cvd

SI p7-8 · Figure S2 discussion · Figure S2

Metal precursorsFe(acac)3 powders in one 110 mm single-opening tube

Linker precursorsHHB powders in one 110 mm single-opening tube

Solventsnone for CVD

AdditivesNH3 vapour from NH3.H2O container

AtmosphereNH3-assisted low-pressure CVD

Temperaturenot separately stated; configuration variant of Fe-HHB CVD

Substrate orientationsubstrate at gap between equal-length tube openings

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHB powders	Not specified	SI p7-8 · Figure S2 discussion · Figure S2
Metal Source	Fe(acac)3 powders	Not specified	SI p7-8 · Figure S2 discussion · Figure S2
Base	NH3.H2O solution	Not specified	SI p7-8 · Figure S2 discussion · Figure S2

Partial recipeSource: SI

Route 8: Cvd

SI p7 · Figure S2 discussion · Figure S2

Metal precursorsFe(acac)3 powders in longer 160 mm tube

Linker precursorsHHB powders in shorter 65 mm tube

Solventsnone for CVD

AdditivesNH3 vapour from NH3.H2O container

AtmosphereNH3-assisted low-pressure CVD

Temperaturenot separately stated; configuration variant of Fe-HHB CVD

Substrate orientationface-to-face inner tube variant

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHB powders	Not specified	SI p7 · Figure S2 discussion · Figure S2
Metal Source	Fe(acac)3 powders	Not specified	SI p7 · Figure S2 discussion · Figure S2
Base	NH3.H2O solution	Not specified	SI p7 · Figure S2 discussion · Figure S2

Partial recipeSource: SI

Route 9: Other

SI p27 · Figure S21 caption · Figure S21

Metal precursorspreformed Fe-HHB-w thin film

Linker precursorspreformed Fe-HHB-w thin film

AdditivesNH3 atmosphere provided by 14 mol/L NH3.H2O solution

Atmospherehigh-concentration NH3 atmosphere

Temperatureabout 50

Substrate orientationthin film on substrate

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Base	NH3.H2O solution	14 mol/L	SI p27 · Figure S21 caption · Figure S21
Other	freshly-synthesized Fe-HHB-w	Not specified	SI p27 · Figure S21 caption · Figure S21

Partial recipeSource: SI

Route 10: Cvd

SI p8 · Figure S2 discussion · Figure S2

Metal precursorsFe(acac)3 powders on quartz boat

Linker precursorsHHB powders on quartz boat

Solventsnone for CVD

AdditivesNH3 vapour from NH3.H2O container

AtmosphereNH3-assisted low-pressure CVD

Temperaturenot separately stated; configuration variant of Fe-HHB CVD

Substrate orientationconventional quartz boats without face-to-face inner tube system

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHB powders	Not specified	SI p8 · Figure S2 discussion · Figure S2
Metal Source	Fe(acac)3 powders	Not specified	SI p8 · Figure S2 discussion · Figure S2
Base	NH3.H2O solution	Not specified	SI p8 · Figure S2 discussion · Figure S2

Complete recipeSource: Both

Route 11: Cvd

SI p2 · CVD growth of 2D c-CPs thin films · Figure S1

Metal precursors20 mg Fe(acac)3 powders, iron(III) acetylacetonate

Linker precursors2 mg HHB powders, hexahydroxybenzene

Solventsnone for CVD; substrates cleaned with acetone, ethanol and DI water

AdditivesNH3 vapour released from 0.14 mol/L NH3.H2O solution for optimal Fe-HHB-w growth

Atmosphere200 sccm N2 purge, pumped to low pressure about 0.5 mbar; NH3 vapour introduced

TemperatureHHB zone 200; Fe(acac)3 zone 105; ramp 5 min

Time0.167-6

Substrate orientationSiO2/Si or quartz substrates placed in the longer tube about 70 mm from HHB powder

Work-upCool down to room temperature before stopping the pump.

Scalability contextUniform films over about 1 cm2 substrate areas; compatible with device fabrication.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHB powders (HHB = hexahydroxybenzene, TCI Deutschland GmbH)	2 mg	SI p2 · CVD growth of 2D c-CPs thin films · Figure S1
Metal Source	Fe(acac)3 powders (iron(III) acetylacetonate, BLD Pharmatech GmbH)	20 mg	SI p2 · CVD growth of 2D c-CPs thin films · Figure S1
Base	NH3.H2O solution diluted from 25% ammonia solution	container with small syringe-needle opening · 0.14 mol/L for optimal Fe-HHB-w; broader range 1.4 mmol/L to 14 mol/L	SI p2 · CVD growth of 2D c-CPs thin films · Figure S1
Other	N2 purge gas	200 sccm	SI p2 · CVD growth of 2D c-CPs thin films · Figure S1