Synthesis · Macrocyclic ligand-driven ion selectivity and high surface area in a 2D conductive MOF

10 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Other

208 · Post-synthetic metalation of Cu-EP

Metal precursorsCsNO3

Linker precursorspristine Cu-EP

Solventsmethanol/water (20:1 v/v)

Atmosphereroom temperature; atmosphere not specified

Temperatureroom temperature

Time3

Oxidant / reductantCsNO3 described as oxidizing Cs salt

Work-upcentrifugation; washed with acetone twice (10 mL)

Activationdried in vacuum oven at 20 mTorr and 60 C for 1 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Pristine Cu-EP	20 mg, 0.025 mmol ligand pocket	208 · Post-synthetic metalation of Cu-EP
Metal Source	CsNO3	0.5 equiv · 10 mM	208 · Post-synthetic metalation of Cu-EP
Solvent	methanol/water	10 mL, 20:1 v/v	208 · Post-synthetic metalation of Cu-EP

Complete recipeSource: Both

Route 2: Other

208 · Post-synthetic metalation of Cu-EP

Metal precursorsCsNO3

Linker precursorspristine Cu-EP

Solventsmethanol/water (20:1 v/v)

Atmosphereroom temperature; atmosphere not specified

Temperatureroom temperature

Time3

Oxidant / reductantCsNO3 described as oxidizing Cs salt

Work-upcentrifugation; washed with acetone twice (10 mL)

Activationdried in vacuum oven at 20 mTorr and 60 C for 1 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Pristine Cu-EP	20 mg, 0.025 mmol ligand pocket	208 · Post-synthetic metalation of Cu-EP
Metal Source	CsNO3	1 equiv · 10 mM	208 · Post-synthetic metalation of Cu-EP
Solvent	methanol/water	10 mL, 20:1 v/v	208 · Post-synthetic metalation of Cu-EP

Complete recipeSource: Both

Route 3: Other

208 · Post-synthetic metalation of Cu-EP

Metal precursorsCsNO3

Linker precursorspristine Cu-EP

Solventsmethanol/water (20:1 v/v)

Atmosphereroom temperature; atmosphere not specified

Temperatureroom temperature

Time3

Oxidant / reductantCsNO3 described as oxidizing Cs salt

Work-upcentrifugation; washed with acetone twice (10 mL)

Activationdried in vacuum oven at 20 mTorr and 60 C for 1 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Pristine Cu-EP	20 mg, 0.025 mmol ligand pocket	208 · Post-synthetic metalation of Cu-EP
Metal Source	CsNO3	2 equiv · 10 mM	208 · Post-synthetic metalation of Cu-EP
Solvent	methanol/water	10 mL, 20:1 v/v	208 · Post-synthetic metalation of Cu-EP

Complete recipeSource: Both

Route 4: Other

208 · Post-synthetic metalation of Cu-EP

Metal precursorsCsOAc

Linker precursorspristine Cu-EP

Solventsmethanol/water (20:1 v/v)

Atmosphereroom temperature; atmosphere not specified

Temperatureroom temperature

Time3

Oxidant / reductantCsOAc described as non-oxidizing Cs salt

Work-upcentrifugation; washed with acetone twice (10 mL)

Activationdried in vacuum oven at 20 mTorr and 60 C for 1 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Pristine Cu-EP	20 mg, 0.025 mmol ligand pocket	208 · Post-synthetic metalation of Cu-EP
Metal Source	CsOAc	2 equiv	208 · Post-synthetic metalation of Cu-EP
Solvent	methanol/water	10 mL, 20:1 v/v	208 · Post-synthetic metalation of Cu-EP

Complete recipeSource: Both

Route 5: Drop Cast

S3 · Electrochemical characterization

Solventsethanol

AdditivesSuper P; PTFE

Atmosphereambient

Temperature65

Time0.25

Substrate orientationglassy carbon electrode

Work-updrop-cast ink; dried at 65 C for 15 min

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-EP	7.5 mg in SI method; 75 wt% in main text	S3 · Electrochemical characterization
Additive	Super P	1.0 mg; 10 wt%	S3 · Electrochemical characterization
Additive	PTFE	1.5 mg; 15 wt%	S3 · Electrochemical characterization
Solvent	ethanol	250 uL in SI method	S3 · Electrochemical characterization

Complete recipeSource: Both

Route 6: Other

208 · Post-synthetic metalation of Cu-EP

Metal precursorsLiNO3

Linker precursorspristine Cu-EP

Solventsmethanol/water (20:1 v/v)

Atmosphereroom temperature; atmosphere not specified

Temperatureroom temperature

Time3

Work-upcentrifugation; washed with acetone twice (10 mL)

Activationdried in vacuum oven at 20 mTorr and 60 C for 1 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Pristine Cu-EP	20 mg, 0.025 mmol ligand pocket	208 · Post-synthetic metalation of Cu-EP
Metal Source	LiNO3	2 equiv	208 · Post-synthetic metalation of Cu-EP
Solvent	methanol/water	10 mL, 20:1 v/v	208 · Post-synthetic metalation of Cu-EP

Complete recipeSource: Both

Route 7: Solvothermal

208 · Synthesis of Cu-EP

Metal precursorsCu(NO3)2.2.5H2O

Linker precursorsEP ligand

Solventsdegassed DMF; water additive

Additives0.4 mL water

Atmosphereinert atmosphere

Temperature60

Time12

Work-upcooled to room temperature; centrifuged; washed with DMF (2 x 10 mL) and acetone (2 x 10 mL)

Activationdried in vacuum oven at 20 mTorr and 70 C for 1 h

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	EP ligand	10 mg, 0.0145 mmol	208 · Synthesis of Cu-EP
Metal Source	Cu(NO3)2.2.5H2O	5 mg, 0.0217 mmol	208 · Synthesis of Cu-EP
Solvent	degassed DMF	10 mL	208 · Synthesis of Cu-EP
Base	water	0.4 mL	208 · Synthesis of Cu-EP

Complete recipeSource: SI

Route 8: Drop Cast

S3 · Electrochemical characterization

Solventsethanol

AdditivesSuper P; PTFE

Atmosphereambient

Temperature65

Time0.25

Substrate orientationglassy carbon electrode

Work-updrop-cast ink; dried at 65 C for 15 min

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-HHTC	included in 7.5 mg MOF ink recipe	S3 · Electrochemical characterization
Additive	Super P	1.0 mg	S3 · Electrochemical characterization
Additive	PTFE	1.5 mg	S3 · Electrochemical characterization
Solvent	ethanol	250 uL	S3 · Electrochemical characterization

Complete recipeSource: SI

Route 9: Solvothermal

S25 · Synthesis of Cu-HHTC

Metal precursorsCu(NO3)2.2.5H2O

Linker precursorsHHTC ligand

Solventsdegassed DMF and degassed H2O

Atmospheredegassed solvents; atmosphere not otherwise specified

Temperature50

Time8

Work-upcentrifugation; washed with DMF (2 x 10 mL), then acetone (2 x 10 mL)

Activationdried in vacuum oven at 20 mTorr and 70 C for 1 h

Scalability contextReported method from earlier work; reproduced here for control sample.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTC ligand	10 mg, 0.025 mmol	S25 · Synthesis of Cu-HHTC
Metal Source	Cu(NO3)2.2.5H2O	11.7 mg, 0.05 mmol	S25 · Synthesis of Cu-HHTC
Solvent	degassed DMF	5 mL	S25 · Synthesis of Cu-HHTC
Solvent	degassed H2O	5 mL	S25 · Synthesis of Cu-HHTC

Complete recipeSource: SI

Route 10: Other

S6-S12 · Synthesis of macrocyclic ethynylphenanthrene (EP) · Scheme S1

Linker precursors3,6-dibromo-9,10-phenanthrenedione; compound 1; compound 2; compound 3

Solventstoluene/ethylene glycol; tetrahydrofuran/piperidine; toluene; trifluoroacetic acid/water; tetrahydrofuran/water

Additivesp-toluenesulfonic acid; PdCl2(PPh3)2; CuI; catalyst ligand/precursor for Mo catalyst; 5 A molecular sieves; sodium thiosulfate

Atmospheredegassed/inert atmosphere specified for later steps

Temperature130; 60; 50; room temperature

Time24; overnight; 48; 24 plus 48

Oxidant / reductantsodium thiosulfate

Work-upfiltration, washing, brine wash, MgSO4 drying, concentration, chromatography, Celite, hot ethyl acetate, water quench

Scalability contextAuthors state modified acetal-protected route gave approximately 51% overall yield and is practically more useful for MOF synthesis.

Show 9 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	3,6-Dibromo-9,10-phenanthrenedione	3.66 g, 10 mmol	S6-S12 · Synthesis of macrocyclic ethynylphenanthrene (EP) · Scheme S1
Solvent	toluene and ethylene glycol	150 mL mixture, 1:1 v/v	S6-S12 · Synthesis of macrocyclic ethynylphenanthrene (EP) · Scheme S1
Acid	p-Toluenesulfonic acid	172 mg, 1 mmol	S6-S12 · Synthesis of macrocyclic ethynylphenanthrene (EP) · Scheme S1
Additive	1-pentyne	0.78 mL, 7.5 mmol	S6-S12 · Synthesis of macrocyclic ethynylphenanthrene (EP) · Scheme S1
Additive	PdCl2(PPh3)2	0.213 g, 0.3 mmol, 10 mol%	S6-S12 · Synthesis of macrocyclic ethynylphenanthrene (EP) · Scheme S1
Additive	CuI	0.056 g, 0.30 mmol, 10 mol%	S6-S12 · Synthesis of macrocyclic ethynylphenanthrene (EP) · Scheme S1
Solvent	tetrahydrofuran and piperidine	25 mL mixture, 4:1 v/v	S6-S12 · Synthesis of macrocyclic ethynylphenanthrene (EP) · Scheme S1
Additive	5 A molecular sieves	1.0 g	S6-S12 · Synthesis of macrocyclic ethynylphenanthrene (EP) · Scheme S1
Reductant	sodium thiosulfate	0.95 g, 6 mmol	S6-S12 · Synthesis of macrocyclic ethynylphenanthrene (EP) · Scheme S1