Synthesis · Oxidative control over the morphology of Cu3(HHTP)2, a 2D conductive metal-organic framework

7 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Solvothermal

S5 · Control Syntheses

Metal precursorsCuSO4*5H2O, 89.8 mg, 360 umol, 2.29 equiv

Linker precursorshexahydroxytriphenylene, 51.0 mg, 157 umol, 1.00 equiv

SolventsDMF 0.60 mL; H2O 4.80 mL; wash solvents H2O, ethanol, acetone

Atmosphereair

Temperature80

Time12

Oxidant / reductantair/oxygen as oxidant

Work-upseparate HHTP/solvent and CuSO4 vials heated 5 min at 80 deg C, combined, heated 12 h; centrifugation; washed H2O (2x), ethanol (2x), acetone (4x); filtered and stored in inert-atmosphere box

Activationnone reported

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	*CuSO45H2O, 89.8 mg, 360 umol, 2.29 equiv**	see precursor_metals	S5 · Control Syntheses
Linker	hexahydroxytriphenylene, 51.0 mg, 157 umol, 1.00 equiv	see precursor_linkers	S5 · Control Syntheses
Solvent	DMF 0.60 mL; H2O 4.80 mL; wash solvents H2O, ethanol, acetone	see solvents	S5 · Control Syntheses
Oxidant	air/oxygen as oxidant	see oxidant_reductant	S5 · Control Syntheses

Complete recipeSource: SI

Route 2: Hydrothermal

S5 · Control Syntheses

Metal precursorsCu2(OAc)4*H2O, 0.52 mL of 15.0 mg/mL in H2O, 39.1 umol, 1.81 equiv

Linker precursorshexahydroxytriphenylene, 7.0 mg, 22 umol, 1.0 equiv

SolventsH2O 0.98 mL plus metal solution; wash solvents H2O, ethanol, acetone

Atmosphereair

Temperature80

Time6

Oxidant / reductantair/oxygen as oxidant

Work-upsonicated 5 min at room temperature; centrifugation; washed H2O (2x), ethanol (2x), acetone (4x); filtered and stored in inert-atmosphere box

Activationnone reported

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	*Cu2(OAc)4H2O, 0.52 mL of 15.0 mg/mL in H2O, 39.1 umol, 1.81 equiv**	see precursor_metals	S5 · Control Syntheses
Linker	hexahydroxytriphenylene, 7.0 mg, 22 umol, 1.0 equiv	see precursor_linkers	S5 · Control Syntheses
Solvent	H2O 0.98 mL plus metal solution; wash solvents H2O, ethanol, acetone	see solvents	S5 · Control Syntheses
Oxidant	air/oxygen as oxidant	see oxidant_reductant	S5 · Control Syntheses

Complete recipeSource: SI

Route 3: Solvothermal

S4-S5 · Synthesis of Rod, Block, and Flake Morphologies

Metal precursorsCuSO4*5H2O, 0.096 mL of 30.0 mg/mL in H2O, 11.6 umol, 1.50 equiv

Linker precursorspurified HHTP solution, 0.125 mL of 20.0 mg/mL in DMF, 7.70 umol, 1.00 equiv

SolventsDMF 0.300 mL total; H2O 2.60 mL; wash solvents H2O, acetone, ethanol

AdditivesBaSO4 diluent for sublimed quinone

Atmosphereinert-atmosphere glovebox; washed/analyzed in air after synthesis

Temperature80

Time24

Oxidant / reductant2,5-dichloro-1,4-benzoquinone pre-oxidant, 0.102 mL of 4.00 mg/mL in DMF, 23.1 umol, 0.300 equiv; 2,6-dimethyl-1,4-benzoquinone/BaSO4 sublimed oxidant, 3.00 equiv

Work-upcentrifugation; washed H2O (2x), acetone (3x), ethanol (2x), acetone (4x); filtered and stored in inert atmosphere

Activationnone reported for synthesis; gas sorption samples activated at 80 deg C under dynamic vacuum for 20 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	*CuSO45H2O, 0.096 mL of 30.0 mg/mL in H2O, 11.6 umol, 1.50 equiv**	see precursor_metals	S4-S5 · Synthesis of Rod, Block, and Flake Morphologies
Linker	purified HHTP solution, 0.125 mL of 20.0 mg/mL in DMF, 7.70 umol, 1.00 equiv	see precursor_linkers	S4-S5 · Synthesis of Rod, Block, and Flake Morphologies
Solvent	DMF 0.300 mL total; H2O 2.60 mL; wash solvents H2O, acetone, ethanol	see solvents	S4-S5 · Synthesis of Rod, Block, and Flake Morphologies
Oxidant	2,5-dichloro-1,4-benzoquinone pre-oxidant, 0.102 mL of 4.00 mg/mL in DMF, 23.1 umol, 0.300 equiv; 2,6-dimethyl-1,4-benzoquinone/BaSO4 sublimed oxidant, 3.00 equiv	see oxidant_reductant	S4-S5 · Synthesis of Rod, Block, and Flake Morphologies
Additive	BaSO4 diluent for sublimed quinone	see additives	S4-S5 · Synthesis of Rod, Block, and Flake Morphologies

Complete recipeSource: SI

Route 4: Solvothermal

S5 · Synthesis of Rod, Block, and Flake Morphologies

Metal precursorsCuSO4*5H2O, 0.096 mL of 30.0 mg/mL in H2O, 11.6 umol, 1.50 equiv

Linker precursorspurified HHTP solution, 0.125 mL of 20.0 mg/mL in DMF, 7.70 umol, 1.00 equiv

SolventsDMF 0.300 mL total; H2O 2.60 mL; wash solvents H2O, acetone, ethanol

AdditivesBaSO4 diluent for sublimed quinone

Atmosphereinert-atmosphere glovebox; washed/analyzed in air after synthesis

Temperature80

Time24

Oxidant / reductant2,5-dichloro-1,4-benzoquinone pre-oxidant, 0.085 mL of 8.00 mg/mL in DMF, 38.5 umol, 0.500 equiv; 2,6-dimethyl-1,4-benzoquinone/BaSO4 sublimed oxidant, 3.00 equiv

Work-upcentrifugation; washed H2O (2x), acetone (3x), ethanol (2x), acetone (4x); filtered and stored in inert atmosphere

Activationnone reported for synthesis; gas sorption samples activated at 80 deg C under dynamic vacuum for 20 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	*CuSO45H2O, 0.096 mL of 30.0 mg/mL in H2O, 11.6 umol, 1.50 equiv**	see precursor_metals	S5 · Synthesis of Rod, Block, and Flake Morphologies
Linker	purified HHTP solution, 0.125 mL of 20.0 mg/mL in DMF, 7.70 umol, 1.00 equiv	see precursor_linkers	S5 · Synthesis of Rod, Block, and Flake Morphologies
Solvent	DMF 0.300 mL total; H2O 2.60 mL; wash solvents H2O, acetone, ethanol	see solvents	S5 · Synthesis of Rod, Block, and Flake Morphologies
Oxidant	2,5-dichloro-1,4-benzoquinone pre-oxidant, 0.085 mL of 8.00 mg/mL in DMF, 38.5 umol, 0.500 equiv; 2,6-dimethyl-1,4-benzoquinone/BaSO4 sublimed oxidant, 3.00 equiv	see oxidant_reductant	S5 · Synthesis of Rod, Block, and Flake Morphologies
Additive	BaSO4 diluent for sublimed quinone	see additives	S5 · Synthesis of Rod, Block, and Flake Morphologies

Complete recipeSource: SI

Route 5: Solvothermal

S6 · Control Syntheses

Metal precursorsCuSO4*5H2O, 0.096 mL of 30.0 mg/mL in H2O, 11.6 umol, 1.50 equiv

Linker precursorspurified HHTP solution, 0.125 mL of 20.0 mg/mL in DMF, 7.70 umol, 1.00 equiv

SolventsDMF 0.175 mL; H2O 2.60 mL; wash solvents H2O, acetone, ethanol

Atmosphereinert-atmosphere glovebox / air-free

Temperature80

Time24

Oxidant / reductantno added oxidant

Work-upcentrifugation; washed H2O (2x), acetone (3x), ethanol (2x)

Activationnone reported

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	*CuSO45H2O, 0.096 mL of 30.0 mg/mL in H2O, 11.6 umol, 1.50 equiv**	see precursor_metals	S6 · Control Syntheses
Linker	purified HHTP solution, 0.125 mL of 20.0 mg/mL in DMF, 7.70 umol, 1.00 equiv	see precursor_linkers	S6 · Control Syntheses
Solvent	DMF 0.175 mL; H2O 2.60 mL; wash solvents H2O, acetone, ethanol	see solvents	S6 · Control Syntheses
Oxidant	no added oxidant	see oxidant_reductant	S6 · Control Syntheses

Complete recipeSource: SI

Route 6: Solvothermal

S4 · Synthesis of Rod, Block, and Flake Morphologies

Metal precursorsCuSO4*5H2O, 0.096 mL of 30.0 mg/mL in H2O, 11.6 umol, 1.50 equiv

Linker precursorspurified HHTP solution, 0.125 mL of 20.0 mg/mL in DMF, 7.70 umol, 1.00 equiv

SolventsDMF 0.300 mL total; H2O 2.60 mL; wash solvents H2O, acetone, ethanol

AdditivesBaSO4 diluent for quinone

Atmosphereinert-atmosphere glovebox; washed/analyzed in air after synthesis

Temperature80

Time24

Oxidant / reductant2,6-dimethyl-1,4-benzoquinone/BaSO4, 10.0 wt% quinone, 31.5 mg, 23.1 umol, 3.00 equiv; sublimed oxidant

Work-upcentrifugation; washed H2O (2x), acetone (3x), ethanol (2x), acetone (4x); filtered and stored in inert atmosphere

Activationnone reported for synthesis; gas sorption samples activated at 80 deg C under dynamic vacuum for 20 h

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	*CuSO45H2O, 0.096 mL of 30.0 mg/mL in H2O, 11.6 umol, 1.50 equiv**	see precursor_metals	S4 · Synthesis of Rod, Block, and Flake Morphologies
Linker	purified HHTP solution, 0.125 mL of 20.0 mg/mL in DMF, 7.70 umol, 1.00 equiv	see precursor_linkers	S4 · Synthesis of Rod, Block, and Flake Morphologies
Solvent	DMF 0.300 mL total; H2O 2.60 mL; wash solvents H2O, acetone, ethanol	see solvents	S4 · Synthesis of Rod, Block, and Flake Morphologies
Oxidant	2,6-dimethyl-1,4-benzoquinone/BaSO4, 10.0 wt% quinone, 31.5 mg, 23.1 umol, 3.00 equiv; sublimed oxidant	see oxidant_reductant	S4 · Synthesis of Rod, Block, and Flake Morphologies
Additive	BaSO4 diluent for quinone	see additives	S4 · Synthesis of Rod, Block, and Flake Morphologies

Complete recipeSource: SI

Route 7: Other

S3 · Ligand purification

Metal precursorsnone

Linker precursorsHHTP, 1.19 g, 3.66 mmol

Solventsethyl acetate 75.0 mL; methanol 75.0 mL; water

Additivesactivated charcoal

Atmospherenitrogen purge; nitrogen pillow; vacuum drying

Temperatureroom temperature; 100 deg C and 220 deg C drying

Time18 h reduction stir; 5 min charcoal treatment

Oxidant / reductantsodium dithionite in water, 1.00 M, 22.0 mL, 6.00 equiv

Work-uporganic solvents removed in vacuo; filtered under nitrogen; washed with H2O; charcoal filtration

Activationdried under vacuum at 100 deg C, then in vacuo at 220 deg C

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HHTP, 1.19 g, 3.66 mmol	see precursor_linkers	S3 · Ligand purification
Solvent	ethyl acetate 75.0 mL; methanol 75.0 mL; water	see solvents	S3 · Ligand purification
Reductant	sodium dithionite in water, 1.00 M, 22.0 mL, 6.00 equiv	see oxidant_reductant	S3 · Ligand purification
Additive	activated charcoal	see additives	S3 · Ligand purification