Synthesis · Synthetic Routes for a 2D Semiconductive Copper Hexahydroxybenzene Metal-Organic Framework

5 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Hydrothermal

S3-S4 · Section 2 · Figures S1-S3

Metal precursorsCu(NO3)2.2.5H2O (26.6 mg, 0.33 mmol)

Linker precursorsHexahydroxybenzene (HHB) (10 mg, 0.058 mmol)

SolventsDegassed H2O, 5 mL for copper/en solution plus 5 mL for HHB solution

AdditivesEthylenediamine, 2-10 equivalents to HHB; optimised at 3 equivalents

AtmosphereDegassed water; explicit N2 atmosphere not stated for this small-scale optimisation

TemperatureRT

Time1

Oxidant / reductantNo external oxidant/reductant; HHB undergoes deprotonation/serial oxidation during framework formation according to proposed mechanism.

Work-upFiltered dark navy precipitate; washed with H2O (50 mL x 2) and acetone (25 mL x 2); dried in an 80 C oven.

ActivationNone in this optimisation recipe; separate water post-treatment is used for porosity/most characterisations.

Scalability contextEthylenediamine stoichiometry and reaction time were varied; >4 equivalents caused an unknown phase, and 3 equivalents was selected as optimised condition.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	26.6 mg, 0.33 mmol	S3-S4 · Section 2 · Figures S1-S3
Linker	Hexahydroxybenzene (HHB)	10 mg, 0.058 mmol	S3-S4 · Section 2 · Figures S1-S3
Base	Ethylenediamine	2-10 equiv. to HHB; optimised 3 equiv.	S3-S4 · Section 2 · Figures S1-S3
Solvent	Degassed H2O	10 mL total	S3-S4 · Section 2 · Figures S1-S3

Complete recipeSource: Both

Route 2: Hydrothermal

S5 · Optimized scale up synthesis of Cu-HHB

Metal precursorsCu(NO3)2.2.5H2O (798 mg, 3.44 mmol)

Linker precursorsHexahydroxybenzene (HHB) (300 mg, 1.74 mmol)

SolventsDegassed H2O, 150 mL for copper solution plus 150 mL for HHB solution

AdditivesEthylenediamine (0.35 mL, 5.25 mmol)

AtmosphereN2 protection; HHB transferred via cannula to copper solution

TemperatureRT; dried at 80 C after workup

Time12

Oxidant / reductantNo external oxidant/reductant; HHB is the reduced linker precursor in the proposed oxidative framework-forming pathway.

Work-upFiltered dark navy precipitate; washed with H2O (100 mL x 2) and acetone (50 mL x 2); dried in an 80 C oven.

ActivationFor most characterisations, post-treat Cu-HHB separately with DI water at 60 C for 12 h, then wash and dry at 80 C.

Scalability contextReported as optimised scale-up synthesis using 300 mg HHB and 300 mL total degassed water; main text frames this as overcoming scale-up barriers.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	798 mg, 3.44 mmol	S5 · Optimized scale up synthesis of Cu-HHB
Linker	Hexahydroxybenzene (HHB)	300 mg, 1.74 mmol	S5 · Optimized scale up synthesis of Cu-HHB
Base	Ethylenediamine	0.35 mL, 5.25 mmol	S5 · Optimized scale up synthesis of Cu-HHB
Solvent	Degassed H2O	300 mL total	S5 · Optimized scale up synthesis of Cu-HHB

Complete recipeSource: SI

Route 3: Other

S7-S8 · Post-treatment of Cu-HHB · Figures S6-S9

Metal precursorsCu-HHB pristine/as-synthesised powder (100 mg)

SolventsDI water (200 mL); wash DI water (100 mL x 2) and acetone (50 mL x 2)

AtmosphereNot specified

Temperature60 and 100 C compared; 60 C selected for most characterisations

Time12

Work-upAfter 12 h, filtered; washed with DI water and acetone; dried in oven at 80 C.

ActivationWater washing/post-treatment to remove entrapped species and open measurable porosity.

Scalability contextPost-treatment converted initially non-measurably porous Cu-HHB into measurably porous powder; 60 C treatment outperformed 100 C reflux for the washed product.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Pristine Cu-HHB	100 mg	S7-S8 · Post-treatment of Cu-HHB · Figures S6-S9
Solvent	DI water	200 mL treatment; 100 mL x 2 wash	S7-S8 · Post-treatment of Cu-HHB · Figures S6-S9
Solvent	Acetone	50 mL x 2 wash	S7-S8 · Post-treatment of Cu-HHB · Figures S6-S9

Complete recipeSource: Both

Route 4: Hydrothermal

S10 · Section 4. Synthesis and characterization of Cu-THQ · Figures S11-S12

Metal precursorsCu(NO3)2.2.5H2O (532 mg, 2.29 mmol)

Linker precursorsTetrahydroxyquinone hydrate (THQ) (300 mg, 1.74 mmol)

SolventsDegassed H2O, 100 mL for THQ plus 100 mL for copper/en solution

AdditivesEthylenediamine (0.23 mL, 3.45 mmol)

AtmosphereN2 protection

TemperatureRT; dried at 80 C after workup

Time12

Oxidant / reductantTHQ is the 2e- oxidised HHB intermediate used as a synthetic shortcut; no external oxidant/reductant stated.

Work-upFiltered dark navy precipitate; washed with H2O (100 mL x 2) and acetone (50 mL x 2); dried in an 80 C oven.

ActivationPost-treatment with H2O at 60 C and 100 C evaluated for porosity/spectroscopy, analogous to Cu-HHB.

Scalability contextPXRD was shown for Cu-THQ products from 15 mg to 500 mg scale; the main text highlights lower-cost, air-stable starting material and scalability.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	532 mg, 2.29 mmol	S10 · Section 4. Synthesis and characterization of Cu-THQ · Figures S11-S12
Linker	Tetrahydroxyquinone (THQ)	300 mg, 1.74 mmol	S10 · Section 4. Synthesis and characterization of Cu-THQ · Figures S11-S12
Base	Ethylenediamine	0.23 mL, 3.45 mmol	S10 · Section 4. Synthesis and characterization of Cu-THQ · Figures S11-S12
Solvent	Degassed H2O	200 mL total	S10 · Section 4. Synthesis and characterization of Cu-THQ · Figures S11-S12

Partial recipeSource: SI

Route 5: Other

S12-S13 · Section 4 · Figures S15-S17

Metal precursorsCu-THQ powder

SolventsH2O treatment at 60 C or 100 C; full volume not separately stated for Cu-THQ, inferred as same post-treatment comparison format as Cu-HHB

AtmosphereNot specified

Temperature60 and 100 C compared

Time12 inferred by analogy to Cu-HHB post-treatment; not restated in the Cu-THQ figure captions

Work-upNot restated; post-treatment evaluated by N2 sorption, FT-IR and TGA.

ActivationWater post-treatment to remove entrapped species/open porosity.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu-THQ	not stated	S12-S13 · Section 4 · Figures S15-S17
Solvent	H2O	not stated	S12-S13 · Section 4 · Figures S15-S17