Synthesis · Highly Porous, Electrically Conductive Two-Dimensional Nickel–Hexaaminodehydrobenzoannulene Frameworks

12 structured synthesis routes

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

Partial recipeSource: SI

Route 1: Other

S4 · S1-1 General information

Metal precursorsNi(OAc)2.4H2O as in reaction mixture

Linker precursorscorresponding ligand hydrochloride

SolventsDMF/water reaction solution

AdditivesNaOAc

Atmosphereair

Temperature50

Substrate orientationhorizontal immersion in custom Teflon holder

Oxidant / reductantair oxidation possible during framework formation

Work-uptop surface cleaned; film grown on bottom side washed with water and MeOH; vacuum dried at room temperature

Activationvacuum drying at room temperature

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	not separately specified for film route	S4 · S1-1 General information
Linker	corresponding ligand hydrochloride	not separately specified for film route	S4 · S1-1 General information
Base	NaOAc	not separately specified for film route	S4 · S1-1 General information
Solvent	DMF/water	not separately specified for film route	S4 · S1-1 General information
Other	fused-silica or ITO/glass substrate	one substrate	S4 · S1-1 General information

Partial recipeSource: SI

Route 2: Other

S4 · S1-1 General information

Metal precursorsNi(OAc)2.4H2O as in reaction mixture

Linker precursorscorresponding ligand hydrochloride

SolventsDMF/water reaction solution

AdditivesNaOAc

Atmosphereair

Temperature50

Substrate orientationvertical immersion

Oxidant / reductantair oxidation possible during framework formation

Work-uptop surface cleaned; film grown on bottom side washed with water and MeOH; vacuum dried at room temperature

Activationvacuum drying at room temperature

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	not separately specified for film route	S4 · S1-1 General information
Linker	corresponding ligand hydrochloride	not separately specified for film route	S4 · S1-1 General information
Base	NaOAc	not separately specified for film route	S4 · S1-1 General information
Solvent	DMF/water	not separately specified for film route	S4 · S1-1 General information
Other	interdigitated gold electrode substrate	one substrate	S4 · S1-1 General information

Partial recipeSource: SI

Route 3: Other

S4 · S1-1 General information

Metal precursorsNi(OAc)2.4H2O as in reaction mixture

Linker precursorscorresponding ligand hydrochloride

SolventsDMF/water reaction solution

AdditivesNaOAc

Atmosphereair

Temperature50

Substrate orientationhorizontal immersion in custom Teflon holder

Oxidant / reductantair oxidation possible during framework formation

Work-uptop surface cleaned; film grown on bottom side washed with water and MeOH; vacuum dried at room temperature

Activationvacuum drying at room temperature

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	not separately specified for film route	S4 · S1-1 General information
Linker	corresponding ligand hydrochloride	not separately specified for film route	S4 · S1-1 General information
Base	NaOAc	not separately specified for film route	S4 · S1-1 General information
Solvent	DMF/water	not separately specified for film route	S4 · S1-1 General information
Other	ITO/glass or fused-silica substrate	one substrate	S4 · S1-1 General information

Complete recipeSource: SI

Route 4: Other

S11 · S1-3 Synthesis

Metal precursorsNi(OAc)2.4H2O (7.0 mg, 28 umol per vial; two mixtures total)

Linker precursorsHA12 hydrochloride (11.3 mg, 19.4 umol per vial)

SolventsDMF (3.0 mL) and distilled water (3.0 mL)

AdditivesNaOAc aqueous solution (4.0 M, 4.0 mL)

Atmosphereair; closed screw vial/oven

Temperature50

Time24

Oxidant / reductantair oxidation possible during framework formation

Work-upfiltration; combined solids washed with water (3 times over 1 day) and MeOH (3 times/day for 2 days)

Activationvacuum drying at room temperature 2 h then 60 C for 2 h

Scalability contextTwo parallel reaction mixtures combined; 14.4 mg, 79% yield.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HA12 hydrochloride	11.3 mg, 19.4 umol per vial	S11 · S1-3 Synthesis
Metal Source	Ni(OAc)2.4H2O	7.0 mg, 28 umol per vial	S11 · S1-3 Synthesis
Base	NaOAc aq	4.0 mL · 4.0 M	S11 · S1-3 Synthesis
Solvent	DMF	3.0 mL	S11 · S1-3 Synthesis
Solvent	distilled water	3.0 mL	S11 · S1-3 Synthesis

Partial recipeSource: SI

Route 5: Other

S4 · S1-1 General information

Metal precursorsNi(OAc)2.4H2O as in reaction mixture

Linker precursorscorresponding ligand hydrochloride

SolventsDMF/water reaction solution

AdditivesNaOAc

Atmosphereair

Temperature50

Substrate orientationhorizontal immersion in custom Teflon holder

Oxidant / reductantair oxidation possible during framework formation

Work-uptop surface cleaned; film grown on bottom side washed with water and MeOH; vacuum dried at room temperature

Activationvacuum drying at room temperature

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	not separately specified for film route	S4 · S1-1 General information
Linker	corresponding ligand hydrochloride	not separately specified for film route	S4 · S1-1 General information
Base	NaOAc	not separately specified for film route	S4 · S1-1 General information
Solvent	DMF/water	not separately specified for film route	S4 · S1-1 General information
Other	fused-silica or ITO/glass substrate	one substrate	S4 · S1-1 General information

Partial recipeSource: SI

Route 6: Other

S4 · S1-1 General information

Metal precursorsNi(OAc)2.4H2O as in reaction mixture

Linker precursorscorresponding ligand hydrochloride

SolventsDMF/water reaction solution

AdditivesNaOAc

Atmosphereair

Temperature50

Substrate orientationvertical immersion

Oxidant / reductantair oxidation possible during framework formation

Work-uptop surface cleaned; film grown on bottom side washed with water and MeOH; vacuum dried at room temperature

Activationvacuum drying at room temperature

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	not separately specified for film route	S4 · S1-1 General information
Linker	corresponding ligand hydrochloride	not separately specified for film route	S4 · S1-1 General information
Base	NaOAc	not separately specified for film route	S4 · S1-1 General information
Solvent	DMF/water	not separately specified for film route	S4 · S1-1 General information
Other	interdigitated gold electrode substrate	one substrate	S4 · S1-1 General information

Partial recipeSource: SI

Route 7: Other

S4 · S1-1 General information

Metal precursorsNi(OAc)2.4H2O as in reaction mixture

Linker precursorscorresponding ligand hydrochloride

SolventsDMF/water reaction solution

AdditivesNaOAc

Atmosphereair

Temperature50

Substrate orientationhorizontal immersion in custom Teflon holder

Oxidant / reductantair oxidation possible during framework formation

Work-uptop surface cleaned; film grown on bottom side washed with water and MeOH; vacuum dried at room temperature

Activationvacuum drying at room temperature

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	not separately specified for film route	S4 · S1-1 General information
Linker	corresponding ligand hydrochloride	not separately specified for film route	S4 · S1-1 General information
Base	NaOAc	not separately specified for film route	S4 · S1-1 General information
Solvent	DMF/water	not separately specified for film route	S4 · S1-1 General information
Other	ITO/glass or fused-silica substrate	one substrate	S4 · S1-1 General information

Complete recipeSource: SI

Route 8: Other

S12 · S1-3 Synthesis

Metal precursorsNi(OAc)2.4H2O (6.9 mg, 28 umol per vial; two mixtures total)

Linker precursorsHA18 hydrochloride (12.6 mg, 20.4 umol per vial)

SolventsDMF (3.0 mL) and distilled water (3.0 mL)

AdditivesNaOAc aqueous solution (4.0 M, 4.0 mL)

Atmosphereair; closed screw vial/oven

Temperature50

Time48

Oxidant / reductantair oxidation possible during framework formation

Work-upfiltration; combined solids washed with water (3 times over 1 day) and MeOH (3 times/day for 2 days)

Activationvacuum drying at room temperature 2 h then 60 C for 2 h

Scalability contextTwo parallel reaction mixtures combined; 14.5 mg, 65% yield.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HA18 hydrochloride	12.6 mg, 20.4 umol per vial	S12 · S1-3 Synthesis
Metal Source	Ni(OAc)2.4H2O	6.9 mg, 28 umol per vial	S12 · S1-3 Synthesis
Base	NaOAc aq	4.0 mL · 4.0 M	S12 · S1-3 Synthesis
Solvent	DMF	3.0 mL	S12 · S1-3 Synthesis
Solvent	distilled water	3.0 mL	S12 · S1-3 Synthesis

Partial recipeSource: SI

Route 9: Other

S4 · S1-1 General information

Metal precursorsNi(OAc)2.4H2O as in reaction mixture

Linker precursorscorresponding ligand hydrochloride

SolventsDMF/water reaction solution

AdditivesNaOAc

Atmosphereair

Temperature50

Substrate orientationhorizontal immersion in custom Teflon holder

Oxidant / reductantair oxidation possible during framework formation

Work-uptop surface cleaned; film grown on bottom side washed with water and MeOH; vacuum dried at room temperature

Activationvacuum drying at room temperature

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	not separately specified for film route	S4 · S1-1 General information
Linker	corresponding ligand hydrochloride	not separately specified for film route	S4 · S1-1 General information
Base	NaOAc	not separately specified for film route	S4 · S1-1 General information
Solvent	DMF/water	not separately specified for film route	S4 · S1-1 General information
Other	fused-silica or ITO/glass substrate	one substrate	S4 · S1-1 General information

Partial recipeSource: SI

Route 10: Other

S4 · S1-1 General information

Metal precursorsNi(OAc)2.4H2O as in reaction mixture

Linker precursorscorresponding ligand hydrochloride

SolventsDMF/water reaction solution

AdditivesNaOAc

Atmosphereair

Temperature50

Substrate orientationvertical immersion

Oxidant / reductantair oxidation possible during framework formation

Work-uptop surface cleaned; film grown on bottom side washed with water and MeOH; vacuum dried at room temperature

Activationvacuum drying at room temperature

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	not separately specified for film route	S4 · S1-1 General information
Linker	corresponding ligand hydrochloride	not separately specified for film route	S4 · S1-1 General information
Base	NaOAc	not separately specified for film route	S4 · S1-1 General information
Solvent	DMF/water	not separately specified for film route	S4 · S1-1 General information
Other	interdigitated gold electrode substrate	one substrate	S4 · S1-1 General information

Partial recipeSource: SI

Route 11: Other

S4 · S1-1 General information

Metal precursorsNi(OAc)2.4H2O as in reaction mixture

Linker precursorscorresponding ligand hydrochloride

SolventsDMF/water reaction solution

AdditivesNaOAc

Atmosphereair

Temperature50

Substrate orientationhorizontal immersion in custom Teflon holder

Oxidant / reductantair oxidation possible during framework formation

Work-uptop surface cleaned; film grown on bottom side washed with water and MeOH; vacuum dried at room temperature

Activationvacuum drying at room temperature

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	not separately specified for film route	S4 · S1-1 General information
Linker	corresponding ligand hydrochloride	not separately specified for film route	S4 · S1-1 General information
Base	NaOAc	not separately specified for film route	S4 · S1-1 General information
Solvent	DMF/water	not separately specified for film route	S4 · S1-1 General information
Other	ITO/glass or fused-silica substrate	one substrate	S4 · S1-1 General information

Complete recipeSource: SI

Route 12: Other

S11 · S1-3 Synthesis

Metal precursorsNi(OAc)2.4H2O (3.5 mg, 14 umol per vial; five mixtures total)

Linker precursorsHATP hydrochloride (5.0 mg, 9.3 umol per vial)

SolventsDMF (1.5 mL) and distilled water (1.5 mL)

AdditivesNaOAc aqueous solution (4.0 M, 2.0 mL)

Atmosphereair; closed screw vial/oven

Temperature50

Time12

Oxidant / reductantair oxidation possible during framework formation

Work-upfiltration; combined solids washed with water (3 times over 1 day) and MeOH (3 times/day for 2 days)

Activationvacuum drying at room temperature 2 h then 60 C for 2 h

Scalability contextFive parallel reaction mixtures combined; 15.1 mg, 75% yield.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATP hydrochloride	5.0 mg, 9.3 umol per vial	S11 · S1-3 Synthesis
Metal Source	Ni(OAc)2.4H2O	3.5 mg, 14 umol per vial	S11 · S1-3 Synthesis
Base	NaOAc aq	2.0 mL · 4.0 M	S11 · S1-3 Synthesis
Solvent	DMF	1.5 mL	S11 · S1-3 Synthesis
Solvent	distilled water	1.5 mL	S11 · S1-3 Synthesis