Synthesis · 2D Rhodium-Isocyanide Frameworks

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

8 · Synthesis of the model compound M1 · Scheme S1

Metal precursors[Rh(COD)Cl]2 (50 mg, 0.10 mmol)

Linker precursors2,6-dimethylphenylisocyanide (iCN-A; 106 mg, 0.81 mmol)

Solventsanhydrous chloroform (20 mL); THF/hexanes for crystal growth

AtmosphereAr

Temperatureroom temperature; -20 C for single-crystal growth

Time2 h reaction

Work-upevaporation; crude product washed with hexanes; single crystals by slow hexane diffusion into THF solution

Scalability context55 mg, 83% yield

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	[Rh(COD)Cl]2	50 mg, 0.10 mmol	8 · Synthesis of the model compound M1 · Scheme S1
Linker	2,6-dimethylphenylisocyanide (iCN-A)	106 mg, 0.81 mmol	8 · Synthesis of the model compound M1 · Scheme S1
Solvent	anhydrous chloroform	20 mL	8 · Synthesis of the model compound M1 · Scheme S1

Complete recipeSource: SI

Route 2: Other

10 · Synthesis of the model compound M2 · Scheme S2

Metal precursors[Rh(COD)Cl]2 (50 mg, 0.10 mmol)

Linker precursorsiCN-B (165 mg, 0.81 mmol)

Solventsanhydrous chloroform (20 mL)

AtmosphereAr

Temperatureroom temperature

Time2 h reaction

Work-upevaporation; crude product washed with methanol and hexanes

Scalability context70 mg, 73% yield

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	[Rh(COD)Cl]2	50 mg, 0.10 mmol	10 · Synthesis of the model compound M2 · Scheme S2
Linker	iCN-B	165 mg, 0.81 mmol	10 · Synthesis of the model compound M2 · Scheme S2
Solvent	anhydrous chloroform	20 mL	10 · Synthesis of the model compound M2 · Scheme S2

Complete recipeSource: Both

Route 3: Other

14 · Synthesis of 2D Rh-iCN MOFs · Scheme S6

Metal precursors[Rh(COD)Cl]2 (50 mg, 0.10 mmol)

Linker precursorsiCN-1 (52.5 mg, 0.41 mmol)

SolventsCHCl3 (20 mL), dried/deoxygenated

AtmosphereAr; inert gas recommended because [Rh(COD)Cl]2 is sensitive to air and water

Temperatureroom temperature

Timeovernight

Work-upsolid separated by filtration, washed with chloroform, dried under vacuum

Activationnone reported for synthesis; porosity sample activation used anhydrous dioxane 12 h then dynamic vacuum at 180 C for 8 h

Scalability context110 mg product, 71% yield; no stirring/disturbance recommended to improve crystallinity

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	[Rh(COD)Cl]2	50 mg, 0.10 mmol	14 · Synthesis of 2D Rh-iCN MOFs · Scheme S6
Linker	iCN-1	52.5 mg, 0.41 mmol	14 · Synthesis of 2D Rh-iCN MOFs · Scheme S6
Solvent	CHCl3	20 mL	14 · Synthesis of 2D Rh-iCN MOFs · Scheme S6

Partial recipeSource: SI

Route 4: Other

7 · Preparation of catalyst ink

Metal precursorsas-synthesised MOF sample

Solvents0.5% Nafion ethanol solution (400 uL)

Additivescarbon black (Cabot VXC-72, 2 mg); Nafion binder

Atmospherenot specified for ink preparation

Temperatureroom temperature

Timestirring overnight plus sonication 0.5 h

Substrate orientationworking electrode support not specified

Work-uphomogeneous dispersion formed; subsequent loading details not specified

Scalability context2 mg MOF + 2 mg carbon black in 400 uL Nafion ethanol solution

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	MOF	2 mg	7 · Preparation of catalyst ink
Additive	carbon black (Cabot VXC-72)	2 mg	7 · Preparation of catalyst ink
Additive	Nafion ethanol solution	400 uL · 0.5%	7 · Preparation of catalyst ink

Complete recipeSource: Both

Route 5: Other

14 · Synthesis of 2D Rh-iCN MOFs · Scheme S6

Metal precursors[Rh(COD)Cl]2 (50 mg, 0.10 mmol)

Linker precursorsiCN-2 (106 mg, 0.41 mmol)

SolventsCHCl3 (20 mL), dried/deoxygenated

AtmosphereAr; inert gas recommended because [Rh(COD)Cl]2 is sensitive to air and water

Temperatureroom temperature

Timeovernight

Work-upsolid separated by filtration, washed with chloroform, dried under vacuum

Activationnone reported for synthesis; porosity sample activation used anhydrous dioxane 12 h then dynamic vacuum at 180 C for 8 h

Scalability context105 mg product, 73% yield; no stirring/disturbance recommended to improve crystallinity

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	[Rh(COD)Cl]2	50 mg, 0.10 mmol	14 · Synthesis of 2D Rh-iCN MOFs · Scheme S6
Linker	iCN-2	106 mg, 0.41 mmol	14 · Synthesis of 2D Rh-iCN MOFs · Scheme S6
Solvent	CHCl3	20 mL	14 · Synthesis of 2D Rh-iCN MOFs · Scheme S6

Partial recipeSource: SI

Route 6: Other

7 · Preparation of catalyst ink

Metal precursorsas-synthesised MOF sample

Solvents0.5% Nafion ethanol solution (400 uL)

Additivescarbon black (Cabot VXC-72, 2 mg); Nafion binder

Atmospherenot specified for ink preparation

Temperatureroom temperature

Timestirring overnight plus sonication 0.5 h

Substrate orientationworking electrode support not specified

Work-uphomogeneous dispersion formed; subsequent loading details not specified

Scalability context2 mg MOF + 2 mg carbon black in 400 uL Nafion ethanol solution

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	MOF	2 mg	7 · Preparation of catalyst ink
Additive	carbon black (Cabot VXC-72)	2 mg	7 · Preparation of catalyst ink
Additive	Nafion ethanol solution	400 uL · 0.5%	7 · Preparation of catalyst ink

Complete recipeSource: Both

Route 7: Other

14 · Synthesis of 2D Rh-iCN MOFs · Scheme S6

Metal precursors[Rh(COD)Cl]2 (50 mg, 0.10 mmol)

Linker precursorsiCN-3 (93 mg, 0.41 mmol)

SolventsCHCl3 (20 mL), dried/deoxygenated

AtmosphereAr; inert gas recommended because [Rh(COD)Cl]2 is sensitive to air and water

Temperatureroom temperature

Timeovernight

Work-upsolid separated by filtration, washed with chloroform, dried under vacuum

Activationnone reported for synthesis; porosity sample activation used anhydrous dioxane 12 h then dynamic vacuum at 180 C for 8 h

Scalability context105 mg product, 70% yield; no stirring/disturbance recommended to improve crystallinity

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	[Rh(COD)Cl]2	50 mg, 0.10 mmol	14 · Synthesis of 2D Rh-iCN MOFs · Scheme S6
Linker	iCN-3	93 mg, 0.41 mmol	14 · Synthesis of 2D Rh-iCN MOFs · Scheme S6
Solvent	CHCl3	20 mL	14 · Synthesis of 2D Rh-iCN MOFs · Scheme S6

Partial recipeSource: SI

Route 8: Other

7 · Preparation of catalyst ink

Metal precursorsas-synthesised MOF sample

Solvents0.5% Nafion ethanol solution (400 uL)

Additivescarbon black (Cabot VXC-72, 2 mg); Nafion binder

Atmospherenot specified for ink preparation

Temperatureroom temperature

Timestirring overnight plus sonication 0.5 h

Substrate orientationworking electrode support not specified

Work-uphomogeneous dispersion formed; subsequent loading details not specified

Scalability context2 mg MOF + 2 mg carbon black in 400 uL Nafion ethanol solution

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	MOF	2 mg	7 · Preparation of catalyst ink
Additive	carbon black (Cabot VXC-72)	2 mg	7 · Preparation of catalyst ink
Additive	Nafion ethanol solution	400 uL · 0.5%	7 · Preparation of catalyst ink