Synthesis · Imparting Functionality and Enhanced Surface Area to a 2D Electrically Conductive MOF via Macrocyclic Linker

8 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

main p.5, article p.10620 · Experimental Section

Metal precursorsCo(NO3)2.6H2O in isopropanol.

Linker precursorsPristine Cu-HHTC, 25 mg, 0.05 mmol ligand pocket.

Solvents5 mL isopropanol for metal nitrate solution.

AtmosphereN2 atmosphere.

Temperatureroom temperature

Time6

Work-upCentrifuge to isolate solid, wash with acetone (10 mL), dry in vacuum oven at 20 mTorr and 70 C for 1 h.

ActivationVacuum dried at 70 C for 1 h.

Scalability contextPostsynthetic treatment on 25 mg MOF scale.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Pristine Cu-HHTC	25 mg, 0.05 mmol ligand pocket	main p.5, article p.10620 · Experimental Section
Metal Source	Co(NO3)2.6H2O	4 equiv · 20 mM	main p.5, article p.10620 · Experimental Section
Solvent	isopropanol	5 mL	main p.5, article p.10620 · Experimental Section

Complete recipeSource: SI

Route 2: Solvothermal

SI pp.S7-S11 · Optimization of Cu-HHTC · Figures S6-S10

Metal precursorsCu(NO3)2.2.5H2O varied between 1.5 and 2 equiv in the stoichiometry screen.

Linker precursorsHHTC ligand (10 mg, 0.025 mmol).

SolventsDegassed DMF and water, with 4:6, 5:5, and 6:4 H2O/DMF solvent composition screens.

AdditivesBase screen used 8 equiv sodium acetate, ammonium hydroxide, ethylenediamine, or no base.

AtmosphereDegassed solvents; otherwise not reported.

Temperature30 for base screen; 50 for stoichiometry and solvent screens

Time6 for base screen; 8 for stoichiometry and solvent screens

Work-upBlack solid isolated by centrifugation, washed with DMF and acetone, dried at 70 C.

ActivationDried at 70 C for further characterisation.

Scalability contextOptimisation experiments use 10 mg linker scale.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTC ligand	10 mg, 0.025 mmol	SI pp.S7-S11 · Optimization of Cu-HHTC · Figures S6-S10
Metal Source	Cu(NO3)2.2.5H2O	11.7 mg, 0.050 mmol, or 1.5-2 equiv in stoichiometry screen	SI pp.S7-S11 · Optimization of Cu-HHTC · Figures S6-S10
Base	sodium acetate, ammonium hydroxide, ethylenediamine, or no base	8 equivalents in base screen	SI pp.S7-S11 · Optimization of Cu-HHTC · Figures S6-S10
Solvent	DMF and water	4-6 mL each in solvent screen	SI pp.S7-S11 · Optimization of Cu-HHTC · Figures S6-S10

Complete recipeSource: Both

Route 3: Solvothermal

main p.5, article p.10619 · Experimental Section

Metal precursorsCu(NO3)2.2.5H2O (11.7 mg, 0.05 mmol; 2 equiv relative to HHTC).

Linker precursorsHHTC ligand (10 mg, 0.025 mmol).

Solvents5 mL degassed DMF and 5 mL degassed H2O (1:1 v/v).

AdditivesNone; base-free optimised condition.

AtmosphereDegassed solvents; reaction atmosphere not otherwise specified.

Temperature50

Time8

Work-upCool to room temperature; isolate black solid by centrifugation; wash 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; porosity samples evacuated at 30 C for 30 min then 80 C for 8 h.

Scalability contextSmall-batch synthesis using 10 mg linker; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTC ligand	10 mg, 0.025 mmol	main p.5, article p.10619 · Experimental Section
Metal Source	Cu(NO3)2.2.5H2O	11.7 mg, 0.05 mmol	main p.5, article p.10619 · Experimental Section
Solvent	degassed DMF	5 mL	main p.5, article p.10619 · Experimental Section
Solvent	degassed H2O	5 mL	main p.5, article p.10619 · Experimental Section

Partial recipeSource: Both

Route 4: Solvothermal

main p.5, article p.10620 · Experimental Section

Metal precursorsCu(NO3)2.2.5H2O (11.7 mg, 0.050 mmol).

Linker precursorsHHTC ligand (10 mg, 0.025 mmol).

Solvents5 mL DMF and 5 mL degassed water.

AdditivesNone; base-free condition.

AtmosphereDegassed water; otherwise not reported.

Temperature30, 40, 50, 60, 70 in optimisation; 30, 40, 50, 60 for particle-size series

Time6 in optimisation temperature screen; same protocol as optimised synthesis for particle-size series except temperature from 30 to 60 C

Work-upCentrifugation, washing with DMF (2 x 10 mL) and acetone (2 x 10 mL), drying at 70 C.

ActivationPorosity samples evacuated at 30 C for 30 min followed by 80 C for 8 h.

Scalability contextTemperature provides particle-size tuning without changing framework composition.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTC ligand	10 mg, 0.025 mmol	main p.5, article p.10620 · Experimental Section
Metal Source	Cu(NO3)2.2.5H2O	11.7 mg, 0.050 mmol	main p.5, article p.10620 · Experimental Section
Solvent	DMF	5 mL	main p.5, article p.10620 · Experimental Section
Solvent	degassed water	5 mL	main p.5, article p.10620 · Experimental Section

Partial recipeSource: Both

Route 5: Other

main p.5, article p.10619 · Postsynthetic Metalation · Figure S30; Tables S8-S9

Metal precursorsNi(NO3)2.6H2O or Co(NO3)2.6H2O by the Cu-HHTC postsynthetic metalation protocol.

Linker precursorsPristine Cu-HHTP control MOF.

SolventsIsopropanol by analogy to Cu-HHTC metalation.

AtmosphereN2 atmosphere by analogy to Cu-HHTC metalation.

Temperatureroom temperature

Time6

Work-upNot repeated for Cu-HHTP; inferred from the Cu-HHTC metalation protocol.

ActivationNot repeated for Cu-HHTP; inferred vacuum drying from Cu-HHTC protocol.

Scalability contextControl treatment; no yield or uptake efficiency reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Pristine Cu-HHTP	Not specified	main p.5, article p.10619 · Postsynthetic Metalation · Figure S30; Tables S8-S9
Metal Source	Ni(NO3)2.6H2O or Co(NO3)2.6H2O	4 equiv inferred from Cu-HHTC protocol · 20 mM inferred from Cu-HHTC protocol	main p.5, article p.10619 · Postsynthetic Metalation · Figure S30; Tables S8-S9
Solvent	isopropanol	5 mL inferred from Cu-HHTC protocol	main p.5, article p.10619 · Postsynthetic Metalation · Figure S30; Tables S8-S9

Complete recipeSource: SI

Route 6: Hydrothermal

SI p.S27 · Synthesis of Cu-HHTP · Figure S30

Metal precursorsCuSO4.5H2O (41 mg, 0.164 mmol).

Linker precursorsHHTP (23.3 mg, 0.72 mmol as reported).

Solvents0.3 mL DMF, 2.4 mL H2O, plus 0.9 mL H2O for metal salt.

AtmosphereNot reported.

Temperature80

Time6

Work-upCentrifuge powder and wash with water, methanol and acetone twice each.

ActivationVacuum oven for 1 h at 60 C before PXRD.

Scalability contextSmall 4 mL vial synthesis; no yield reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP	23.3 mg, 0.72 mmol	SI p.S27 · Synthesis of Cu-HHTP · Figure S30
Metal Source	CuSO4.5H2O	41 mg, 0.164 mmol	SI p.S27 · Synthesis of Cu-HHTP · Figure S30
Solvent	DMF	0.3 mL	SI p.S27 · Synthesis of Cu-HHTP · Figure S30
Solvent	H2O	2.4 mL plus 0.9 mL	SI p.S27 · Synthesis of Cu-HHTP · Figure S30

Complete recipeSource: SI

Route 7: Other

SI pp.S3-S6 · Synthesis of HHTC ligand · Scheme S1

Metal precursorsNone for ligand synthesis.

Linker precursorsCatechol/1,2-dihydroxybenzene converted through protected, iodinated and alkynylated intermediates to HHTC.

SolventsDMF, chloroform, triethylamine, CCl4/CHCl3, acetone, MeOH, hexanes/ethyl acetate, hexanes/dichloromethane.

AdditivesImidazole, tert-butyldimethylsilyl chloride, DMAP, silver trifluoroacetate, iodine, PdCl2(PPh3)2, CuI, alkyne-metathesis catalyst ligand and precursor, 5 Angstrom molecular sieves, HCl.

AtmosphereCompound 4 step used a degassed solution; other atmospheres not reported.

Temperatureroom temperature, 50, 80

Time12; 6; 48; 16 across steps

Oxidant / reductantIodination with iodine/silver trifluoroacetate; acid deprotection with HCl.

Work-upQuench, extraction, filtration, drying over MgSO4, chromatography, Celite filtration, concentration, and washing as step-specific workups.

ActivationNot applicable to free ligand.

Scalability contextOverall yield from 1,2-dihydroxybenzene to HHTC reported as 55%; final deprotection gave 0.520 g HHTC, 85%.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1,2-dihydroxybenzene	1.08 g, 10 mmol	SI pp.S3-S6 · Synthesis of HHTC ligand · Scheme S1
Additive	tert-butyldimethylsilyl chloride	4.52 g, 30 mmol	SI pp.S3-S6 · Synthesis of HHTC ligand · Scheme S1
Additive	silver trifluoroacetate and iodine	1.46 g, 6.60 mmol; 1.67 g, 6.60 mmol	SI pp.S3-S6 · Synthesis of HHTC ligand · Scheme S1
Additive	1-pentyne, PdCl2(PPh3)2, CuI	1 mL, 10 mmol; 0.263 g, 0.37 mmol; 0.047 g, 0.25 mmol	SI pp.S3-S6 · Synthesis of HHTC ligand · Scheme S1
Acid	HCl	conc. 37%, 1.0 mL · 37%	SI pp.S3-S6 · Synthesis of HHTC ligand · Scheme S1

Complete recipeSource: Both

Route 8: Other

main p.5, article p.10620 · Experimental Section

Metal precursorsNi(NO3)2.6H2O in isopropanol.

Linker precursorsPristine Cu-HHTC, 25 mg, 0.05 mmol ligand pocket.

Solvents5 mL isopropanol for metal nitrate solution.

AtmosphereN2 atmosphere.

Temperatureroom temperature

Time6

Work-upCentrifuge to isolate solid, wash with acetone (10 mL), dry in vacuum oven at 20 mTorr and 70 C for 1 h.

ActivationVacuum dried at 70 C for 1 h.

Scalability contextPostsynthetic treatment on 25 mg MOF scale.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Pristine Cu-HHTC	25 mg, 0.05 mmol ligand pocket	main p.5, article p.10620 · Experimental Section
Metal Source	Ni(NO3)2.6H2O	4 equiv · 20 mM	main p.5, article p.10620 · Experimental Section
Solvent	isopropanol	5 mL	main p.5, article p.10620 · Experimental Section