Synthesis · Catalysis-Assisted Synthesis of Two-Dimensional Conductive Metal–Organic Framework Films with Controllable Orientation

8 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Other

3 · Experimental details · Figure S14-S15

Metal precursorsCu(NO3)2 2.25 mM

Linker precursors8OH-TBA 1.125 mM

SolventsDMF/H2O v/v 1:1.5

AdditivesHNO3 0.75 mM; Pt catalyst

AtmosphereO2 for face-on films by general procedure

Temperatureroom temperature

Time1 h

Substrate orientationfilm orientation assessed by XRD

Oxidant / reductantO2/Pt

Work-uprinsed with DMF and methanol; dried under nitrogen

Activationnot reported

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2	2.25 mM	3 · Experimental details · Figure S14-S15
Linker	8OH-TBA	1.125 mM	3 · Experimental details · Figure S14-S15
Acid	HNO3	0.75 mM	3 · Experimental details · Figure S14-S15
Solvent	DMF/H2O	V:V 1/1.5	3 · Experimental details · Figure S14-S15
Oxidant	O2	general face-on purge	3 · Experimental details · Figure S14-S15
Additive	Pt catalyst layer	0.3 nm	3 · Experimental details · Figure S14-S15

Complete recipeSource: Both

Route 2: Other

3 · Experimental details

Metal precursorsCu(NO3)2 2.25 mM general

Linker precursorsHHTP 1.125 mM general

SolventsDMF/H2O v/v 1:15

AdditivesHNO3 0.5 mM; 0.3 nm Pt catalyst

Atmospherestood in air for 15 min

Temperatureroom temperature

Time1 h for Figure 7; up to 24 h growth series

Substrate orientationedge-on layers perpendicular to substrate

Oxidant / reductantair/O2 with Pt catalyst

Work-uprinsed with DMF and methanol; dried under nitrogen

Activationnone for synthesis

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2	2.25 mM general	3 · Experimental details
Linker	HHTP	1.125 mM general	3 · Experimental details
Acid	HNO3	0.5 mM	3 · Experimental details
Solvent	DMF/H2O	V:V 1/15	3 · Experimental details
Oxidant	air/O2	stood in air 15 min	3 · Experimental details
Additive	Pt catalyst layer	0.3 nm	3 · Experimental details

Complete recipeSource: Both

Route 3: Other

3 · Experimental details

Metal precursorsCu(NO3)2 2.25 mM

Linker precursorsHHTP 1.125 mM

SolventsDMF/H2O v/v 1:15

AdditivesHNO3 0.5 mM; 0.3 nm Pt catalyst

AtmosphereO2 purged/saturated for 15 min

Temperatureroom temperature

Time1 h for Figure 2 sample; varied for growth

Substrate orientationface-on layers parallel to substrate

Oxidant / reductantO2/Pt aerobic HHTP oxidation

Work-uprinsed with DMF and methanol; dried under nitrogen

Activationnone for synthesis; sorption samples evacuated at 80 C for 24 h

Scalability contextcompatible with glass, silicon, parylene, PVC, PDMS, cotton and nylon; patterned via Pt masks

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2	2.25 mM	3 · Experimental details
Linker	HHTP	1.125 mM	3 · Experimental details
Acid	HNO3	0.5 mM	3 · Experimental details
Solvent	DMF/H2O	V:V 1/15	3 · Experimental details
Oxidant	O2	purged/saturated 15 min	3 · Experimental details
Additive	Pt catalyst layer	0.3 nm	3 · Experimental details

Complete recipeSource: SI

Route 4: Other

36 · Gas Sensing · Figure S33-S34

Metal precursorsCu(NO3)2 1.125 mM

Linker precursorsHHTP 2.25 mM

SolventsDMF/H2O v/v 1:15

AdditivesHNO3 0.5 mM; Pt catalyst

Atmosphereair-saturated

Temperatureroom temperature

Time0.333 h (20 min)

Substrate orientationedge-on sensor film

Oxidant / reductantair/O2 with Pt

Work-upAu interdigitated electrodes evaporated after growth

Activationnot reported

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2	1.125 mM	36 · Gas Sensing · Figure S33-S34
Linker	HHTP	2.25 mM	36 · Gas Sensing · Figure S33-S34
Acid	HNO3	0.5 mM	36 · Gas Sensing · Figure S33-S34
Solvent	DMF/H2O	V:V 1/15	36 · Gas Sensing · Figure S33-S34
Oxidant	air/O2	air-saturated	36 · Gas Sensing · Figure S33-S34
Additive	Pt catalyst layer	0.3 nm	36 · Gas Sensing · Figure S33-S34

Complete recipeSource: SI

Route 5: Other

36 · Gas Sensing · Figure S33-S34

Metal precursorsCu(NO3)2 1.125 mM

Linker precursorsHHTP 4.5 mM

SolventsDMF/H2O v/v 1:5

AdditivesHNO3 0.5 mM; Pt catalyst

AtmosphereO2-saturated

Temperatureroom temperature

Time0.0111 h (40 s)

Substrate orientationface-on sensor film

Oxidant / reductantO2/Pt

Work-upAu interdigitated electrodes evaporated after growth

Activationnot reported

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2	1.125 mM	36 · Gas Sensing · Figure S33-S34
Linker	HHTP	4.5 mM	36 · Gas Sensing · Figure S33-S34
Acid	HNO3	0.5 mM	36 · Gas Sensing · Figure S33-S34
Solvent	DMF/H2O	V:V 1/5	36 · Gas Sensing · Figure S33-S34
Oxidant	O2	O2-saturated	36 · Gas Sensing · Figure S33-S34
Additive	Pt catalyst layer	0.3 nm	36 · Gas Sensing · Figure S33-S34

Partial recipeSource: SI

Route 6: Other

3 · Experimental details · Figure S29

Metal precursorsNi(OAc)2 2.33 mM

Linker precursorsHATP 0.775 mM

SolventsDMF/DMA/H2O v/v/v 1.5:1.5:1

AdditivesNaOAc 250 mM; Pt catalyst

AtmosphereO2-saturated

Temperatureroom temperature

Timenot specified

Substrate orientationedge-on film

Oxidant / reductantO2/Pt

Work-uprinsed with DMF and methanol; dried under nitrogen

Activationnot reported

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2	2.33 mM	3 · Experimental details · Figure S29
Linker	HATP	0.775 mM	3 · Experimental details · Figure S29
Base	NaOAc	250 mM	3 · Experimental details · Figure S29
Solvent	DMF/DMA/H2O	V:V:V 1.5/1.5/1	3 · Experimental details · Figure S29
Oxidant	O2	O2-saturated	3 · Experimental details · Figure S29
Additive	Pt catalyst layer	0.3 nm	3 · Experimental details · Figure S29

Complete recipeSource: Both

Route 7: Other

3 · Experimental details · Figure 4; Figure S16

Metal precursorsNi(OAc)2 4.67 mM

Linker precursorsHATP 1.55 mM

SolventsDMF/DMA/H2O v/v/v 1.5:1.5:3

AdditivesNaOAc 500 mM; Pt catalyst

AtmosphereO2-saturated

Temperatureroom temperature

Time1 h

Substrate orientationface-on film

Oxidant / reductantO2/Pt

Work-uprinsed with DMF and methanol; dried under nitrogen

Activationnot reported

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2	4.67 mM	3 · Experimental details · Figure 4; Figure S16
Linker	HATP	1.55 mM	3 · Experimental details · Figure 4; Figure S16
Base	NaOAc	500 mM	3 · Experimental details · Figure 4; Figure S16
Solvent	DMF/DMA/H2O	V:V:V 1.5/1.5/3	3 · Experimental details · Figure 4; Figure S16
Oxidant	O2	O2-saturated	3 · Experimental details · Figure 4; Figure S16
Additive	Pt catalyst layer	0.3 nm	3 · Experimental details · Figure 4; Figure S16

Complete recipeSource: SI

Route 8: Other

3 · Experimental details · Figure S12

Metal precursorsZn(OAc)2 2.25 mM

Linker precursorsHHTP 1.125 mM

SolventsDMF/H2O v/v 1:10

AdditivesHAc 2.4 mM; Pt catalyst

AtmosphereO2 for face-on films by general procedure

Temperatureroom temperature

Time0.5 h

Substrate orientationface-on film stated in main text

Oxidant / reductantO2/Pt

Work-uprinsed with DMF and methanol; dried under nitrogen

Activationnot reported

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(OAc)2	2.25 mM	3 · Experimental details · Figure S12
Linker	HHTP	1.125 mM	3 · Experimental details · Figure S12
Acid	HAc	2.4 mM	3 · Experimental details · Figure S12
Solvent	DMF/H2O	V:V 1/10	3 · Experimental details · Figure S12
Oxidant	O2	general face-on purge	3 · Experimental details · Figure S12
Additive	Pt catalyst layer	0.3 nm	3 · Experimental details · Figure S12