Synthesis · Single Crystals of Electrically Conductive Two-Dimensional Metal-Organic Frameworks: Structural and Electrical Transport Properties

6 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

SI p.2 and p.10 · Exfoliation of Cu3(HHTP)2 particles to obtain flakes; SI Figure 6 · SI Figure 6

Metal precursorsParent washed Cu3(HHTP)2 particles.

Linker precursorsParent washed Cu3(HHTP)2 particles.

Solvents10 mL isopropanol, DI water, acetonitrile or n-methylpyrrolidone.

AtmosphereAmbient bath sonication; atmosphere not controlled.

Time1-2 h sonication; 10 min centrifugation

Work-upSamples centrifuged for 10 min; flakes isolated from blue supernatant.

Scalability contextN-methylpyrrolidone produced brown supernatant and presumably dissolved the MOF.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	washed Cu3(HHTP)2 particles	40 mg	SI p.2 and p.10 · Exfoliation of Cu3(HHTP)2 particles to obtain flakes; SI Figure 6 · SI Figure 6
Solvent	isopropanol, DI water, acetonitrile, or n-methylpyrrolidone	10 mL	SI p.2 and p.10 · Exfoliation of Cu3(HHTP)2 particles to obtain flakes; SI Figure 6 · SI Figure 6

Complete recipeSource: SI

Route 2: Other

SI p.2 and p.9 · Synthesis; Supplementary Figure 5 · SI Figure 5

Metal precursorsCopper sulfate pentahydrate (CuSO4.5H2O), 410 mg; SI text says 1.64 mol but mass corresponds to about 1.64 mmol.

Linker precursorsHHTP, 233 mg (0.718 mmol).

SolventsHHTP in 3 mL DMF and 24 mL H2O; copper sulfate in 9 mL H2O.

AtmosphereGlass jar heated in oven; atmosphere not otherwise specified.

Temperature80

Time12

Oxidant / reductantCopper(II) sulfate and dissolved/ambient O2 may participate; no separate oxidant stated.

Work-upResulting blue powder centrifuged and washed in water, ethanol and acetone twice each.

Scalability contextParticles with six-sided cross sections up to 5 um were obtained.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper sulfate pentahydrate (CuSO4 5H2O)	410 mg (SI text: 1.64 mol; likely 1.64 mmol) · in 9 mL H2O	SI p.2 and p.9 · Synthesis; Supplementary Figure 5 · SI Figure 5
Linker	HHTP	233 mg (0.718 mmol) · in 3 mL DMF and 24 mL H2O	SI p.2 and p.9 · Synthesis; Supplementary Figure 5 · SI Figure 5
Solvent	DMF	3 mL	SI p.2 and p.9 · Synthesis; Supplementary Figure 5 · SI Figure 5
Solvent	H2O	33 mL total	SI p.2 and p.9 · Synthesis; Supplementary Figure 5 · SI Figure 5

Complete recipeSource: SI

Route 3: Solvothermal

SI p.2 and p.4-5 · Synthesis; Growth Discussion · Figure 3a

Metal precursorsCopper acetate hydrate (Cu2(OAc)4.H2O), 7.8 mg (0.039 mmol).

Linker precursorsHHTP, 7 mg (0.022 mmol).

Solvents1.5 mL water plus 0.15 mL DMF added dropwise.

AtmosphereCapped 20 mL glass vial; O2 limitation discussed phenomenologically for some Cu3(HHTP)2 syntheses.

Temperature80

Time6

Oxidant / reductantCopper(II) acetate and dissolved/ambient O2 may influence oxidation; no controlled oxidant stated.

Work-upResulting blue powder centrifuged and washed in water, ethanol and acetone twice each.

Scalability contextUsing water or a small amount of cosolvent gave the largest crystals; higher cosolvent gave smaller or no crystals.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate hydrate (Cu2(OAc)4 H2O)	7.8 mg (0.039 mmol)	SI p.2 and p.4-5 · Synthesis; Growth Discussion · Figure 3a
Linker	HHTP	7 mg (0.022 mmol)	SI p.2 and p.4-5 · Synthesis; Growth Discussion · Figure 3a
Solvent	water	1.5 mL	SI p.2 and p.4-5 · Synthesis; Growth Discussion · Figure 3a
Solvent	DMF	0.15 mL · added dropwise	SI p.2 and p.4-5 · Synthesis; Growth Discussion · Figure 3a

Complete recipeSource: SI

Route 4: Drop Cast

SI p.4 · Device fabrication · Figure 3c; SI Figure 7

SolventsEthanol suspension of rods or flakes.

AdditivesMMA/PMMA resists; Ti/Pd contacts.

AtmosphereVacuum oven bake; e-beam evaporation.

Temperature85 for resist bake

Time5 min resist bake

Substrate orientationSi substrates with pre-patterned marks; contacts deposited on top of rods or flakes.

Work-upDrop-cast onto Si substrates, coat 2 MMA layers and 1 PMMA layer, bake, e-beam lithography at 30 kV, evaporate 3 nm Ti / 250 nm Pd.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Solvent	ethanol	rod or flake suspension	SI p.4 · Device fabrication · Figure 3c; SI Figure 7
Additive	MMA and PMMA	2 layers MMA and 1 layer PMMA	SI p.4 · Device fabrication · Figure 3c; SI Figure 7
Other	Ti/Pd contacts	3 nm Ti / 250 nm Pd	SI p.4 · Device fabrication · Figure 3c; SI Figure 7

Complete recipeSource: SI

Route 5: Drop Cast

SI p.4 · Device fabrication · Figure 2a; SI Figure 4

SolventsEthanol suspension of rods.

AdditivesMMA/PMMA resists; Ti/Pd contacts.

AtmosphereVacuum oven bake; e-beam evaporation.

Temperature85 for resist bake

Time5 min resist bake

Substrate orientationSi substrates with pre-patterned marks; contacts deposited on top of rods.

Work-upDrop-cast onto Si substrates, coat 2 MMA layers and 1 PMMA layer, bake, e-beam lithography at 30 kV, evaporate 3 nm Ti / 250 nm Pd.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Solvent	ethanol	rod suspension	SI p.4 · Device fabrication · Figure 2a; SI Figure 4
Additive	MMA and PMMA	2 layers MMA and 1 layer PMMA	SI p.4 · Device fabrication · Figure 2a; SI Figure 4
Other	Ti/Pd contacts	3 nm Ti / 250 nm Pd	SI p.4 · Device fabrication · Figure 2a; SI Figure 4

Complete recipeSource: SI

Route 6: Other

SI p.2 and p.4-5 · Synthesis; Growth Discussion · SI Figure 1

Metal precursorsNickel chloride hexahydrate (NiCl2.6H2O), 4 mg (0.017 mmol) in 3 mL water.

Linker precursorsHATP.6HCl, 3 mg (0.006 mmol) in 3 mL water.

SolventsWater, 9 mL total across nickel, linker and sodium acetate solutions.

AdditivesSodium acetate, 75 mg (0.914 mmol) in 3 mL water.

AtmosphereOpen vial; SI growth discussion says Ni3(HITP)2 was not obtained in the absence of air and scale-up requires air bubbling.

Temperature60

Time2

Oxidant / reductantAir/O2 implicated as ligand oxidant by growth discussion; not quantified.

Work-upResulting black powder centrifuged and washed in water, ethanol and acetone twice each.

Scalability contextScale-up requires air bubbling; excessive ligand oxidation before MOF formation can give small or no crystals.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel chloride hexahydrate (NiCl2 6H2O)	4 mg (0.017 mmol) · in 3 mL water	SI p.2 and p.4-5 · Synthesis; Growth Discussion · SI Figure 1
Linker	HATP 6HCl	3 mg (0.006 mmol) · in 3 mL water	SI p.2 and p.4-5 · Synthesis; Growth Discussion · SI Figure 1
Base	sodium acetate	75 mg (0.914 mmol) · in 3 mL water	SI p.2 and p.4-5 · Synthesis; Growth Discussion · SI Figure 1
Solvent	water	9 mL total	SI p.2 and p.4-5 · Synthesis; Growth Discussion · SI Figure 1
Oxidant	air/O2	open vial; air bubbling needed for scale-up	SI p.2 and p.4-5 · Synthesis; Growth Discussion · SI Figure 1