Synthesis · Diverse π-π Stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal-organic frameworks

3 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Solvothermal

S3-S4 · Experimental Methods · Scheme 1; synthesis of La4(HTTFTB)4 (1)

Metal precursorsLa(NO3)3.6H2O, 5.2 mg, 0.012 mmol

Linker precursorsH4TTFTB, 8.2 mg, 0.012 mmol

Solvents0.93 mL 1:1 H2O/EtOH for La salt; 0.47 mL 3:1 DMF/EtOH for linker; Scheme 1: 25% DMF, 33% H2O, 42% EtOH

Additivesnone reported

Atmospheresolvothermal atmosphere not specified; supercritical CO2-activated product stored in argon-filled glovebox

Temperature50

Time24

Oxidant / reductantnone reported

Work-upwashed with 3 x 2 mL EtOH

Activationsupercritical CO2 drying; EtOH soak 24 h with 3 solution changes, liquid CO2 exchange, about 40 deg C/1300 psi, vent 8 h, then 50 deg C dynamic vacuum 8 h

Scalability contextbulk polycrystalline powder recipe in 2 mL vial; no scale-up demonstrated

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	La(NO3)3.6H2O	5.2 mg, 0.012 mmol	S3-S4 · Experimental Methods · Scheme 1; synthesis of La4(HTTFTB)4 (1)
Linker	H4TTFTB	8.2 mg, 0.012 mmol	S3-S4 · Experimental Methods · Scheme 1; synthesis of La4(HTTFTB)4 (1)
Solvent	H2O/EtOH	0.93 mL of 1:1 mixture	S3-S4 · Experimental Methods · Scheme 1; synthesis of La4(HTTFTB)4 (1)
Solvent	DMF/EtOH	0.47 mL of 3:1 mixture	S3-S4 · Experimental Methods · Scheme 1; synthesis of La4(HTTFTB)4 (1)
Other	CO2	supercritical drying medium	S3-S4 · Experimental Methods · Scheme 1; synthesis of La4(HTTFTB)4 (1)

Complete recipeSource: Both

Route 2: Solvothermal

S3 · Experimental Methods · Scheme 1; synthesis of La(HTTFTB) (2)

Metal precursorsLa(NO3)3.6H2O, 10.9 mg, 0.0252 mmol

Linker precursorsH4TTFTB, 8.6 mg, 0.013 mmol

Solvents0.70 mL 1:1 H2O/EtOH for La salt; 0.70 mL 3:1 DMF/EtOH for linker; Scheme 1: 37.5% DMF, 25% H2O, 37.5% EtOH

Additivesnone reported

Atmospheresolvothermal atmosphere not specified; activated under dynamic vacuum

Temperature60

Time72

Oxidant / reductantnone reported

Work-upwashed with 3 x 2 mL DMF and 3 x 2 mL EtOH

Activationheated to 220 deg C under dynamic vacuum for 24 h

Scalability contextbulk polycrystalline powder recipe in 2 mL vial; no scale-up demonstrated

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	La(NO3)3.6H2O	10.9 mg, 0.0252 mmol	S3 · Experimental Methods · Scheme 1; synthesis of La(HTTFTB) (2)
Linker	H4TTFTB	8.6 mg, 0.013 mmol	S3 · Experimental Methods · Scheme 1; synthesis of La(HTTFTB) (2)
Solvent	H2O/EtOH	0.70 mL of 1:1 mixture	S3 · Experimental Methods · Scheme 1; synthesis of La(HTTFTB) (2)
Solvent	DMF/EtOH	0.70 mL of 3:1 mixture	S3 · Experimental Methods · Scheme 1; synthesis of La(HTTFTB) (2)

Complete recipeSource: Both

Route 3: Solvothermal

S3-S4 · Experimental Methods · Scheme 1; synthesis of La4(TTFTB)3 (3)

Metal precursorsLa(NO3)3.6H2O, 7.8 mg, 0.018 mmol

Linker precursorsH4TTFTB, 11.1 mg, 0.0162 mmol

Solvents0.50 mL 1:1 H2O/EtOH for La salt; 0.90 mL 3:1 DMF/EtOH for linker; Scheme 1: 48% DMF, 18% H2O, 34% EtOH

Additivesnone reported

Atmospheresolvothermal atmosphere not specified; supercritical CO2-activated product stored in argon-filled glovebox

Temperature65

Time72

Oxidant / reductantnone reported

Work-upwashed with 3 x 2 mL DMF and 3 x 2 mL EtOH

Activationsupercritical CO2 drying; EtOH soak 24 h with 3 solution changes, liquid CO2 exchange, about 40 deg C/1300 psi, vent 8 h, then 50 deg C dynamic vacuum 8 h

Scalability contextbulk polycrystalline powder recipe in 2 mL vial; no scale-up demonstrated

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	La(NO3)3.6H2O	7.8 mg, 0.018 mmol	S3-S4 · Experimental Methods · Scheme 1; synthesis of La4(TTFTB)3 (3)
Linker	H4TTFTB	11.1 mg, 0.0162 mmol	S3-S4 · Experimental Methods · Scheme 1; synthesis of La4(TTFTB)3 (3)
Solvent	H2O/EtOH	0.50 mL of 1:1 mixture	S3-S4 · Experimental Methods · Scheme 1; synthesis of La4(TTFTB)3 (3)
Solvent	DMF/EtOH	0.90 mL of 3:1 mixture	S3-S4 · Experimental Methods · Scheme 1; synthesis of La4(TTFTB)3 (3)
Other	CO2	supercritical drying medium	S3-S4 · Experimental Methods · Scheme 1; synthesis of La4(TTFTB)3 (3)