Synthesis · From 2D to 3D: Postsynthetic Pillar Insertion in Electrically Conductive MOF

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

SI p.S7 · Varying stoichiometry of BPY to copper centers · Figure S6

Metal precursorsPreformed Cu-THQ, 10 mg.

Linker precursors4,4'-bipyridyl (BPY), 8.9 mg; Cu2+:BPY = 1:1.

SolventsDI H2O, 5 mL.

AtmosphereAir/ambient atmosphere not explicitly specified.

Temperatureroom temperature

Time24

Work-upCentrifuged at 3000 rpm for 7 min; supernatant decanted; washed with H2O, methanol twice and acetone twice.

ActivationVacuum oven at 60 C for 1 h.

Scalability context20 mL reaction vial; no yield reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-THQ	10 mg	SI p.S7 · Varying stoichiometry of BPY to copper centers · Figure S6
Linker	BPY	8.9 mg · Cu2+:BPY = 1:1	SI p.S7 · Varying stoichiometry of BPY to copper centers · Figure S6
Solvent	DI H2O	5.0 mL	SI p.S7 · Varying stoichiometry of BPY to copper centers · Figure S6

Complete recipeSource: Both

Route 2: Other

SI p.S7 · Varying stoichiometry of BPY to copper centers · Figure S6

Metal precursorsPreformed Cu-THQ, 10 mg.

Linker precursors4,4'-bipyridyl (BPY), 17.6 mg; Cu2+:BPY = 1:2.

SolventsDI H2O, 5 mL.

AtmosphereAir/ambient atmosphere not explicitly specified.

Temperatureroom temperature

Time24

Work-upCentrifuged at 3000 rpm for 7 min; supernatant decanted; washed with H2O, methanol twice and acetone twice.

ActivationVacuum oven at 60 C for 1 h.

Scalability context20 mL reaction vial; no yield reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-THQ	10 mg	SI p.S7 · Varying stoichiometry of BPY to copper centers · Figure S6
Linker	BPY	17.6 mg · Cu2+:BPY = 1:2	SI p.S7 · Varying stoichiometry of BPY to copper centers · Figure S6
Solvent	DI H2O	5.0 mL	SI p.S7 · Varying stoichiometry of BPY to copper centers · Figure S6

Complete recipeSource: Both

Route 3: Other

main p.6 · Experimental Section - BPY Insertion

Metal precursorsPreformed Cu-THQ, 10 mg.

Linker precursors4,4'-bipyridyl (BPY), 4.5 mg; Cu2+:BPY = 2:1.

SolventsH2O, 5 mL.

AtmosphereAir/ambient atmosphere not explicitly specified for insertion; room temperature.

Temperatureroom temperature

Time24

Work-upCentrifuged at 3000 rpm for 7 min; supernatant decanted; washed twice with 5 mL H2O, twice with 5 mL methanol, and twice with 5 mL acetone.

ActivationVacuum oven at 60 C for 1 h.

Scalability context20 mL reaction vial; no yield reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-THQ	10 mg	main p.6 · Experimental Section - BPY Insertion
Linker	BPY	4.5 mg · Cu2+:BPY = 2:1	main p.6 · Experimental Section - BPY Insertion
Solvent	H2O	5 mL	main p.6 · Experimental Section - BPY Insertion

Complete recipeSource: Main

Route 4: Other

main p.6 · Experimental Section - Synthesis of Cu-THQ

Metal precursorsCu(NO3)2.2.5H2O, 177 mg, 0.76 mmol.

Linker precursorsTetrahydroxybenzoquinone (THQ), 100 mg, 0.58 mmol.

SolventsDegassed H2O, 33 mL for Cu/ethylenediamine solution plus 33 mL for THQ solution.

AdditivesEthylenediamine, 76 uL, 1.15 mmol.

AtmosphereN2 atmosphere; degassed water.

Temperatureroom temperature

Time9

Work-upDark navy precipitate filtered; washed with H2O (50 mL x2), methanol (50 mL x2) and acetone (50 mL x2).

ActivationDried in a 65 C oven for 2 h.

Scalability contextBench-scale solution precipitation; isolated yield not reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	177 mg, 0.76 mmol	main p.6 · Experimental Section - Synthesis of Cu-THQ
Additive	ethylenediamine	76 uL, 1.15 mmol	main p.6 · Experimental Section - Synthesis of Cu-THQ
Solvent	degassed H2O	33 mL + 33 mL	main p.6 · Experimental Section - Synthesis of Cu-THQ
Linker	THQ	100 mg, 0.58 mmol	main p.6 · Experimental Section - Synthesis of Cu-THQ

Complete recipeSource: SI

Route 5: Drop Cast

SI p.S14 · Electrochemical performance

Metal precursorsCu-THQ powder already synthesised.

Linker precursorsTHQ present in Cu-THQ.

SolventsEthanol, 0.15 mL; 1 M KOH electrolyte used during measurement.

AdditivesPTFE binder solution, 0.75 mg, 60 wt% in H2O; carbon black, 0.5 mg.

AtmosphereAir drying/oven drying not otherwise specified.

Temperature65

Time0.5

Substrate orientationGlassy carbon working electrode, radius 1.5 mm.

Work-upMOF ink ground to a homogeneous slurry; 40 uL drop-cast onto glassy carbon.

ActivationDried for 30 min in a 65 C oven.

Scalability contextElectrode preparation for electrochemical testing; not a standalone MOF synthesis.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-THQ MOF powder	5 mg	SI p.S14 · Electrochemical performance
Additive	PTFE binder solution	0.75 mg · 60 wt% in H2O	SI p.S14 · Electrochemical performance
Additive	carbon black	0.5 mg	SI p.S14 · Electrochemical performance
Solvent	ethanol	0.15 mL	SI p.S14 · Electrochemical performance

Complete recipeSource: SI

Route 6: Drop Cast

SI p.S14 · Electrochemical performance

Metal precursorsCu-THQ-BPY powder already prepared.

Linker precursorsTHQ and BPY present in Cu-THQ-BPY.

SolventsEthanol, 0.15 mL; 1 M KOH electrolyte used during measurement.

AdditivesPTFE binder solution, 0.75 mg, 60 wt% in H2O; carbon black, 0.5 mg.

AtmosphereAir drying/oven drying not otherwise specified.

Temperature65

Time0.5

Substrate orientationGlassy carbon working electrode, radius 1.5 mm.

Work-upMOF ink ground to a homogeneous slurry; 40 uL drop-cast onto glassy carbon.

ActivationDried for 30 min in a 65 C oven.

Scalability contextElectrode preparation for electrochemical testing; not a standalone MOF synthesis.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-THQ-BPY MOF powder	5 mg	SI p.S14 · Electrochemical performance
Additive	PTFE binder solution	0.75 mg · 60 wt% in H2O	SI p.S14 · Electrochemical performance
Additive	carbon black	0.5 mg	SI p.S14 · Electrochemical performance
Solvent	ethanol	0.15 mL	SI p.S14 · Electrochemical performance

Complete recipeSource: SI

Route 7: Other

SI p.S6 · Physically mixing of Cu-THQ and BPY · Figure S5

Metal precursorsPreformed Cu-THQ powder, 5 mg.

Linker precursorsBPY, 4.5 mg.

AtmosphereAmbient.

Temperatureroom temperature

Time0.083

Work-upGround in an agate mortar until a homogeneous powder mixture formed.

ActivationNo drying or activation reported.

Scalability contextSmall physical-mixture control; not a framework synthesis.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-THQ powder	5 mg	SI p.S6 · Physically mixing of Cu-THQ and BPY · Figure S5
Linker	BPY	4.5 mg	SI p.S6 · Physically mixing of Cu-THQ and BPY · Figure S5

Complete recipeSource: Main

Route 8: Other

main p.6 · Experimental Section - PYZ Insertion

Metal precursorsPreformed Cu-THQ, 35 mg.

Linker precursorsPyrazine (PYZ), 16.2 mg; Cu2+:PYZ = 1:1.

SolventsH2O, 17.5 mL; methanol and acetone for washing.

AtmosphereAir/ambient atmosphere not explicitly specified.

Temperatureroom temperature

Time24

Work-upCentrifuged at 3000 rpm for 7 min; washed with 15 mL water; soaked in 25 mL methanol twice for 30 min and once overnight; washed with 10 mL acetone.

ActivationVacuum oven at 60 C for 1 h.

Scalability context50 mL Erlenmeyer flask; no yield reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-THQ	35 mg	main p.6 · Experimental Section - PYZ Insertion
Linker	PYZ	16.2 mg · Cu2+:PYZ = 1:1	main p.6 · Experimental Section - PYZ Insertion
Solvent	H2O	17.5 mL	main p.6 · Experimental Section - PYZ Insertion