Synthesis · Iodine-induced electrical conductivity of novel columnar lanthanide metal-organic frameworks based on a butterfly-shaped π-extended tetrathiafulvalene ligand

4 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

p002 / SI page S2 · Synthesis of Ln-MOFs

Metal precursorsEr(NO3)3.5H2O (0.0135 mmol)

Linker precursorsExTTFTB ligand (8.6 mg, 0.010 mmol)

SolventsDMF (1.0 mL for ligand) plus 2:1 DMF/H2O mixture (1.5 mL for metal salt) plus chlorobenzene (1 mL)

Additivestrifluoroacetic acid (TFA, 0.1 mL)

Atmospherescrew-capped vial; atmosphere not otherwise specified

Temperature65

Time72

Work-upWashed thoroughly with DMF, solvent-exchanged with EtOH, then dried under vacuum for 48 h.

ActivationVacuum drying for 48 h after EtOH solvent exchange.

Scalability contextSmall-vial solvothermal preparation; no scale-up reported.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Er(NO3)3.5H2O	0.0135 mmol	p002 / SI page S2 · Synthesis of Ln-MOFs
Linker	ExTTFTB ligand	8.6 mg, 0.010 mmol	p002 / SI page S2 · Synthesis of Ln-MOFs
Solvent	DMF	1.0 mL plus part of 1.5 mL 2:1 DMF/H2O mixture	p002 / SI page S2 · Synthesis of Ln-MOFs
Solvent	H2O	part of 1.5 mL 2:1 DMF/H2O mixture	p002 / SI page S2 · Synthesis of Ln-MOFs
Acid	TFA	0.1 mL	p002 / SI page S2 · Synthesis of Ln-MOFs
Solvent	chlorobenzene	1 mL	p002 / SI page S2 · Synthesis of Ln-MOFs

Complete recipeSource: Both

Route 2: Solvothermal

p002 / SI page S2 · Synthesis of Ln-MOFs

Metal precursorsEu(NO3)3.5H2O (0.0135 mmol)

Linker precursorsExTTFTB ligand (8.6 mg, 0.010 mmol)

SolventsDMF (1.0 mL for ligand) plus 2:1 DMF/H2O mixture (1.5 mL for metal salt) plus chlorobenzene (1 mL)

Additivestrifluoroacetic acid (TFA, 0.1 mL)

Atmospherescrew-capped vial; atmosphere not otherwise specified

Temperature65

Time72

Work-upWashed thoroughly with DMF, solvent-exchanged with EtOH, then dried under vacuum for 48 h.

ActivationVacuum drying for 48 h after EtOH solvent exchange.

Scalability contextSmall-vial solvothermal preparation; no scale-up reported.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Eu(NO3)3.5H2O	0.0135 mmol	p002 / SI page S2 · Synthesis of Ln-MOFs
Linker	ExTTFTB ligand	8.6 mg, 0.010 mmol	p002 / SI page S2 · Synthesis of Ln-MOFs
Solvent	DMF	1.0 mL plus part of 1.5 mL 2:1 DMF/H2O mixture	p002 / SI page S2 · Synthesis of Ln-MOFs
Solvent	H2O	part of 1.5 mL 2:1 DMF/H2O mixture	p002 / SI page S2 · Synthesis of Ln-MOFs
Acid	TFA	0.1 mL	p002 / SI page S2 · Synthesis of Ln-MOFs
Solvent	chlorobenzene	1 mL	p002 / SI page S2 · Synthesis of Ln-MOFs

Complete recipeSource: Both

Route 3: Other

p002 / SI page S2 · Iodine-Treated Tb-MOF

Metal precursorspreformed evacuated Tb-MOF powder (20 mg)

Linker precursorsExTTFTB ligand already incorporated in Tb-MOF

Atmospheresealed larger screw-capped vial containing iodine chips; iodine vapour exposure

Temperatureambient/not specified

Time96

Oxidant / reductantiodine chips / I2 vapour oxidant

Work-upWashed thoroughly with hexanes and kept under vacuum to remove physisorbed iodide.

ActivationVacuum treatment after hexane wash.

Scalability contextPost-synthetic vapour treatment of 20 mg powder; no scale-up reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	evacuated Tb-MOF powder	20 mg	p002 / SI page S2 · Iodine-Treated Tb-MOF
Oxidant	iodine chips	a few iodine chips	p002 / SI page S2 · Iodine-Treated Tb-MOF
Solvent	hexanes	wash solvent; amount not reported	p002 / SI page S2 · Iodine-Treated Tb-MOF

Complete recipeSource: Both

Route 4: Solvothermal

p002 / SI page S2 · Synthesis of Ln-MOFs

Metal precursorsTb(NO3)3.5H2O (0.0135 mmol)

Linker precursorsExTTFTB ligand (8.6 mg, 0.010 mmol)

SolventsDMF (1.0 mL for ligand) plus 2:1 DMF/H2O mixture (1.5 mL for metal salt) plus chlorobenzene (1 mL)

Additivestrifluoroacetic acid (TFA, 0.1 mL)

Atmospherescrew-capped vial; atmosphere not otherwise specified

Temperature65

Time72

Work-upWashed thoroughly with DMF, solvent-exchanged with EtOH, then dried under vacuum for 48 h.

ActivationVacuum drying for 48 h after EtOH solvent exchange.

Scalability contextSmall-vial solvothermal preparation; no scale-up reported.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Tb(NO3)3.5H2O	0.0135 mmol	p002 / SI page S2 · Synthesis of Ln-MOFs
Linker	ExTTFTB ligand	8.6 mg, 0.010 mmol	p002 / SI page S2 · Synthesis of Ln-MOFs
Solvent	DMF	1.0 mL plus part of 1.5 mL 2:1 DMF/H2O mixture	p002 / SI page S2 · Synthesis of Ln-MOFs
Solvent	H2O	part of 1.5 mL 2:1 DMF/H2O mixture	p002 / SI page S2 · Synthesis of Ln-MOFs
Acid	TFA	0.1 mL	p002 / SI page S2 · Synthesis of Ln-MOFs
Solvent	chlorobenzene	1 mL	p002 / SI page S2 · Synthesis of Ln-MOFs