Synthesis · Electrically Conductive π-Intercalated Graphitic Metal-Organic Framework Containing Alternate π-Donor/Acceptor Stacks

6 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

S4 · Cu3(HATP)2

Metal precursorsCu(NO3)2.3H2O (6.75 mg, 0.03 mmol, 2 mL aqueous solution)

Linker precursorsHATP.6HCl (10 mg, 0.02 mmol, 2 mL DMF)

SolventsDMF and water

AdditivesNaOAc (2 M, 2 mL aqueous solution)

AtmosphereOpen glass vial

Temperatureroom temperature

Time5 min sonication, then 4 h stirring

Work-upCentrifuged; washed thoroughly with water and acetone; dried under vacuum.

ActivationVacuum dried for further studies; N2 sorption used activated Cu3(HATP)2 but activation protocol not specified.

Scalability contextPrepared under the same conditions as iGMOF1 for direct comparison.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATP.6HCl	10 mg, 0.02 mmol	S4 · Cu3(HATP)2
Solvent	DMF	2 mL	S4 · Cu3(HATP)2
Metal Source	Cu(NO3)2.3H2O	6.75 mg, 0.03 mmol, 2 mL	S4 · Cu3(HATP)2
Base	NaOAc	2 mL · 2 M	S4 · Cu3(HATP)2

Complete recipeSource: SI

Route 2: Other

S4 · HCTP-Treated Cu3(HATP)2 · Figure S5c

Linker precursorsPreformed Cu3(HATP)2 powder (50 mg); HCTP in DMF

SolventsDMF; acetone for washing

AtmosphereNot specified

Temperatureroom temperature

Time72 h soaking

Work-upCentrifuged; washed with DMF and acetone; dried under vacuum.

ActivationDried under vacuum.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3(HATP)2 powder	50 mg	S4 · HCTP-Treated Cu3(HATP)2 · Figure S5c
Other	HCTP DMF solution	5 mL · 100 mM	S4 · HCTP-Treated Cu3(HATP)2 · Figure S5c
Solvent	DMF	5 mL solution plus wash	S4 · HCTP-Treated Cu3(HATP)2 · Figure S5c
Solvent	acetone	wash	S4 · HCTP-Treated Cu3(HATP)2 · Figure S5c

Complete recipeSource: SI

Route 3: Other

S4 · Cu3(HATP)2 in the Presence of pi-Donors Pyrene and Triphenylene

Metal precursorsCu(NO3)2.3H2O (6.75 mg, 0.03 mmol, 2 mL aqueous solution)

Linker precursorsHATP (10 mg, 0.02 mmol) and pyrene (3.8 mg, approximately 0.02 mmol) in DMF

SolventsDMF and water

AdditivesNaOAc (2 M, 2 mL aqueous solution)

AtmosphereOpen glass vial

Temperatureroom temperature

Time5 min sonication, then 4 h stirring

Work-upCentrifuged; washed thoroughly with water and acetone; dried under vacuum.

ActivationDried under vacuum.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATP	10 mg, 0.02 mmol	S4 · Cu3(HATP)2 in the Presence of pi-Donors Pyrene and Triphenylene
Other	pyrene	3.8 mg, approximately 0.02 mmol	S4 · Cu3(HATP)2 in the Presence of pi-Donors Pyrene and Triphenylene
Metal Source	Cu(NO3)2.3H2O	6.75 mg, 0.03 mmol, 2 mL	S4 · Cu3(HATP)2 in the Presence of pi-Donors Pyrene and Triphenylene
Base	NaOAc	2 mL · 2 M	S4 · Cu3(HATP)2 in the Presence of pi-Donors Pyrene and Triphenylene

Complete recipeSource: SI

Route 4: Other

S4 · Cu3(HATP)2 in the Presence of pi-Donors Pyrene and Triphenylene

Metal precursorsCu(NO3)2.3H2O (6.75 mg, 0.03 mmol, 2 mL aqueous solution)

Linker precursorsHATP (10 mg, 0.02 mmol) and triphenylene (TP, 4.3 mg, approximately 0.02 mmol) in DMF

SolventsDMF and water

AdditivesNaOAc (2 M, 2 mL aqueous solution)

AtmosphereOpen glass vial

Temperatureroom temperature

Time5 min sonication, then 4 h stirring

Work-upCentrifuged; washed thoroughly with water and acetone; dried under vacuum.

ActivationDried under vacuum.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATP	10 mg, 0.02 mmol	S4 · Cu3(HATP)2 in the Presence of pi-Donors Pyrene and Triphenylene
Other	triphenylene (TP)	4.3 mg, approximately 0.02 mmol	S4 · Cu3(HATP)2 in the Presence of pi-Donors Pyrene and Triphenylene
Metal Source	Cu(NO3)2.3H2O	6.75 mg, 0.03 mmol, 2 mL	S4 · Cu3(HATP)2 in the Presence of pi-Donors Pyrene and Triphenylene
Base	NaOAc	2 mL · 2 M	S4 · Cu3(HATP)2 in the Presence of pi-Donors Pyrene and Triphenylene

Partial recipeSource: SI

Route 5: Other

S4 · Supramolecular [HATP/HCTP]n Array

Linker precursorsHATP (10 mg, 0.02 mmol) and HCTP (7.15 mg, 0.02 mmol)

SolventsDMF; Et2O for precipitation

AtmosphereNot specified

Temperatureroom temperature

TimeImmediate mixing; slow evaporation time not specified

Work-upSlow DMF evaporation for crystals; or Et2O precipitation, Et2O wash, and vacuum drying for powder.

ActivationDried under vacuum.

Scalability contextReported isolated powder yield 14.45 mg (85%).

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATP	10 mg, 0.02 mmol	S4 · Supramolecular [HATP/HCTP]n Array
Other	HCTP	7.15 mg, 0.02 mmol	S4 · Supramolecular [HATP/HCTP]n Array
Solvent	DMF	1 mL for each solution	S4 · Supramolecular [HATP/HCTP]n Array
Solvent	Et2O	not specified	S4 · Supramolecular [HATP/HCTP]n Array

Complete recipeSource: Both

Route 6: Other

S4 · iGMOF1 · Scheme 1

Metal precursorsCu(NO3)2.3H2O (6.75 mg, 0.03 mmol, 2 mL aqueous solution)

Linker precursorsHATP (10 mg, 0.02 mmol, 1 mL DMF); HCTP (7.15 mg, 0.02 mmol, 1 mL DMF)

SolventsDMF and water

AdditivesNaOAc (2 M, 2 mL aqueous solution)

AtmosphereAir/open glass vial after metal/base addition; screw-capped glass vial during initial HATP/HCTP mixing

Temperatureroom temperature

Time0.5 h pre-assembly, then 4 h stirring after Cu(NO3)2/NaOAc addition

Work-upCentrifuged; washed thoroughly with water and acetone; dried under vacuum.

ActivationVacuum dried for further studies; N2 sorption used evacuated iGMOF1 but evacuation protocol not specified.

Scalability contextNear-quantitative yield reported; batch scale in SI used 10 mg HATP.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATP	10 mg, 0.02 mmol	S4 · iGMOF1 · Scheme 1
Other	HCTP	7.15 mg, 0.02 mmol	S4 · iGMOF1 · Scheme 1
Solvent	DMF	1 mL for HATP plus 1 mL for HCTP	S4 · iGMOF1 · Scheme 1
Metal Source	Cu(NO3)2.3H2O	6.75 mg, 0.03 mmol, 2 mL	S4 · iGMOF1 · Scheme 1
Base	NaOAc	2 mL · 2 M	S4 · iGMOF1 · Scheme 1