Synthesis · Air/liquid interfacial formation process of conductive metal–organic framework nanosheets

9 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

S3-S4 · Synthesis of a 2,3,6,7,10,11-hexaaminotriphenylene (HATP) ligand

Linker precursors2,3,6,7,10,11-hexabromotriphenylene (HBTP)

Solventstoluene; dichloromethane; hexane/ethyl acetate; dehydrated fresh THF; hexane wash

AdditivesPd2(dba)3, rac-BINAP, benzophenone imine, sodium tert-butoxide, aqueous HCl

AtmosphereN2 for coupling and hydrolysis; HBPIT stored under Ar

Temperature104 C preheat; 100 C coupling; about 30 C cooling; room-temperature hydrolysis/workup

Time0.5 h preheat at 104 C; >12 h coupling at 100 C; 0.5 h after HCl addition; overnight vacuum drying

Work-upCelite filtration, silica-gel chromatography with hexane/ethyl acetate 4/1, rotary evaporation, THF and hexane centrifuge washes, vacuum drying.

ActivationStored in Ar glove box until use.

Scalability contextRepresentative ligand batch gave 213.44 mg HATP.6HCl, 0.397 mmol, 55 percent yield.

Show 8 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HBTP	1.0391 g, 1.48 mmol	S3-S4 · Synthesis of a 2,3,6,7,10,11-hexaaminotriphenylene (HATP) ligand
Additive	Pd2(dba)3	0.3335 g, 0.36 mmol	S3-S4 · Synthesis of a 2,3,6,7,10,11-hexaaminotriphenylene (HATP) ligand
Additive	rac-BINAP	0.4519 g, 0.73 mmol	S3-S4 · Synthesis of a 2,3,6,7,10,11-hexaaminotriphenylene (HATP) ligand
Solvent	toluene	37 mL	S3-S4 · Synthesis of a 2,3,6,7,10,11-hexaaminotriphenylene (HATP) ligand
Additive	benzophenone imine	2 mL, 11.13 mmol	S3-S4 · Synthesis of a 2,3,6,7,10,11-hexaaminotriphenylene (HATP) ligand
Base	sodium tert-butoxide	1.1123 g, 11.57 mmol	S3-S4 · Synthesis of a 2,3,6,7,10,11-hexaaminotriphenylene (HATP) ligand
Solvent	dehydrated fresh THF	42.4 mL	S3-S4 · Synthesis of a 2,3,6,7,10,11-hexaaminotriphenylene (HATP) ligand
Acid	aqueous HCl	1.874 mL · 3.0 M	S3-S4 · Synthesis of a 2,3,6,7,10,11-hexaaminotriphenylene (HATP) ligand

Partial recipeSource: SI

Route 2: Air Liquid Interface

S5 · Synthesis of HATP-water-NS at air/liquid interfaces

Linker precursorsHATP solution in methanol

Solventsmethanol; pure water

Atmosphereroom temperature

Temperatureroom temperature

Time1 h standing before compression

Substrate orientationPTFE Langmuir trough, air/water interface

Work-upSurface compressed with two PTFE barriers at 10 mm min-1 while surface pressure was recorded.

Scalability contextTrough 375 x 75 mm2.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATP	Not specified	S5 · Synthesis of HATP-water-NS at air/liquid interfaces
Solvent	methanol	Not specified	S5 · Synthesis of HATP-water-NS at air/liquid interfaces
Solvent	pure water	Not specified	S5 · Synthesis of HATP-water-NS at air/liquid interfaces

Partial recipeSource: Both

Route 3: Air Liquid Interface

5 (journal p. 773) · 3.1.1 In-situ observation

Metal precursorsNi(OAc)2.4H2O aqueous solution, 50 mM

Linker precursorsHATP methanol solution, 0.59 mM

Solventsmethanol; aqueous Ni(OAc)2.4H2O solution

Atmosphereroom temperature in air

Temperature20-21 C subphase; room temperature

Timestanding time 2 h after about 10 min HATP spreading

Substrate orientationLangmuir-Schaefer horizontal transfer

Work-upSurface compressed with PTFE barriers; transferred at pi = 5 mN m-1 for many ex-situ measurements; Si/quartz rinsed in pure water for 10 s and dried with N2.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	50 mM	5 (journal p. 773) · 3.1.1 In-situ observation
Linker	HATP.6HCl (abbreviated as HATP)	0.59 mM	5 (journal p. 773) · 3.1.1 In-situ observation

Partial recipeSource: Both

Route 4: Air Liquid Interface

5 (journal p. 773) · 3.1.1 In-situ observation

Metal precursorsNi(OAc)2.4H2O aqueous solution, 50 mM

Linker precursorsHATP methanol solution, 0.59 mM

Solventsmethanol; aqueous Ni(OAc)2.4H2O solution

Atmosphereroom temperature in air

Temperature20-21 C subphase; room temperature

Timestanding time 3 h after about 10 min HATP spreading

Substrate orientationLangmuir-Schaefer horizontal transfer

Work-upSurface compressed with PTFE barriers; transferred at pi = 5 mN m-1 for many ex-situ measurements; Si/quartz rinsed in pure water for 10 s and dried with N2.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	50 mM	5 (journal p. 773) · 3.1.1 In-situ observation
Linker	HATP.6HCl (abbreviated as HATP)	0.59 mM	5 (journal p. 773) · 3.1.1 In-situ observation

Partial recipeSource: Both

Route 5: Air Liquid Interface

5 (journal p. 773) · 3.1.1 In-situ observation

Metal precursorsNi(OAc)2.4H2O aqueous solution, 50 mM

Linker precursorsHATP methanol solution, 0.59 mM

Solventsmethanol; aqueous Ni(OAc)2.4H2O solution

Atmosphereroom temperature in air

Temperature20-21 C subphase; room temperature

Timestanding time 4 h after about 10 min HATP spreading

Substrate orientationLangmuir-Schaefer horizontal transfer

Work-upSurface compressed with PTFE barriers; transferred at pi = 5 mN m-1 for many ex-situ measurements; Si/quartz rinsed in pure water for 10 s and dried with N2.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	50 mM	5 (journal p. 773) · 3.1.1 In-situ observation
Linker	HATP.6HCl (abbreviated as HATP)	0.59 mM	5 (journal p. 773) · 3.1.1 In-situ observation

Partial recipeSource: Both

Route 6: Air Liquid Interface

5 (journal p. 773) · 3.1.1 In-situ observation

Metal precursorsNi(OAc)2.4H2O aqueous solution, 50 mM

Linker precursorsHATP methanol solution, 0.59 mM

Solventsmethanol; aqueous Ni(OAc)2.4H2O solution

Atmosphereroom temperature in air

Temperature20-21 C subphase; room temperature

Timestanding time 1 h after about 10 min HATP spreading

Substrate orientationLangmuir-Schaefer horizontal transfer

Work-upSurface compressed with PTFE barriers; transferred at pi = 5 mN m-1 for many ex-situ measurements; Si/quartz rinsed in pure water for 10 s and dried with N2.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	50 mM	5 (journal p. 773) · 3.1.1 In-situ observation
Linker	HATP.6HCl (abbreviated as HATP)	0.59 mM	5 (journal p. 773) · 3.1.1 In-situ observation

Partial recipeSource: Both

Route 7: Air Liquid Interface

3 (journal p. 771) · 2.2 Fabrication of HITP-Ni-NS at the air/liquid interface

Metal precursorsNi(OAc)2.4H2O aqueous solution, 50 mM

Linker precursorsHATP.6HCl, abbreviated as HATP, methanol solution 0.59 mM

Solventsmethanol; aqueous Ni(OAc)2.4H2O solution

Atmosphereroom temperature in air

Temperature20-21 C subphase; room temperature

TimeHATP spreading about 10 min; standing time varied 1-300 min; selected sample 1 min

Substrate orientationLangmuir-Schaefer horizontal substrate approach for transfer; Si, quartz and Cu grids used depending on measurement.

Work-upAfter reaching standing time, surface compressed with PTFE barriers at 10 mm min-1; samples transferred at selected surface pressure. Si/quartz substrates immersed in pure water for 10 s to remove unreacted metal ions and dried with N2.

Scalability contextPTFE Langmuir trough surface area reported as 318 x 75 mm2 in main text; SI gives 375 x 75 mm2 for related control preparations. HATP solution volume was not explicitly reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	50 mM	3 (journal p. 771) · 2.2 Fabrication of HITP-Ni-NS at the air/liquid interface
Linker	HATP.6HCl (abbreviated as HATP)	0.59 mM	3 (journal p. 771) · 2.2 Fabrication of HITP-Ni-NS at the air/liquid interface
Solvent	methanol	Not specified	3 (journal p. 771) · 2.2 Fabrication of HITP-Ni-NS at the air/liquid interface
Solvent	water	filled Langmuir trough until meniscus visually confirmed	3 (journal p. 771) · 2.2 Fabrication of HITP-Ni-NS at the air/liquid interface

Partial recipeSource: SI

Route 8: Air Liquid Interface

S5 · Synthesis of HITP-Ni_subphase at air/liquid interfaces

Metal precursorsNi(OAc)2.4H2O aqueous solution, 50 mM

Linker precursorsHATP solution in methanol, 0.59 mM

Solventsmethanol; aqueous Ni(OAc)2.4H2O solution

Atmosphereroom temperature

Temperatureroom temperature

Time4 h after HATP spreading

Substrate orientationPTFE Langmuir trough; barrier fixed to create space outside barriers

Scalability contextTrough 375 x 75 mm2; area inside barriers 150 x 75 mm2.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	50 mM	S5 · Synthesis of HITP-Ni_subphase at air/liquid interfaces
Linker	HATP	0.59 mM	S5 · Synthesis of HITP-Ni_subphase at air/liquid interfaces

Vague recipeSource: SI

Route 9: Unknown

S6 · Synthesis of Ni3(HITP)2 bulk powder