Synthesis · The Advent of Electrically Conducting Double-Helical Metal-Organic Frameworks Featuring Butterfly-Shaped Electron-Rich π-Extended Tetrathiafulvalene Ligands

5 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

S-3 · Synthesis and Characterization of Ligands and dhMOF

Metal precursorsZn(NO3)2.6H2O

Linker precursorsExTTFTB ligand

Solvents3:1 DMF/EtOH solution plus separately prepared 1:1 EtOH/H2O metal-source solution; overall main-text solvent ratio 3:3:2 DMF/EtOH/H2O

AtmosphereScrew-capped vial; no inert atmosphere specified for MOF assembly

Temperature65

Time24

Work-upMetal solution added slowly to ligand solution with no immediate precipitation; orange plate crystals washed thoroughly with the same solvent mixture; solvent exchange with EtOH; dried under vacuum for 48 h.

ActivationFor CO2 sorption, as-synthesised crystals were soaked in EtOH for 5 days with daily refresh, then evacuated under high vacuum initially at room temperature and then at 120 deg C for 24 h.

Scalability contextBulk dhMOF powder isolated as 47 mg, 83% yield based on ExTTFTB ligand.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	ExTTFTB ligand	43 mg, 0.05 mmol	S-3 · Synthesis and Characterization of Ligands and dhMOF
Metal Source	Zn(NO3)2.6H2O	55 mg, 0.19 mmol	S-3 · Synthesis and Characterization of Ligands and dhMOF
Solvent	DMF/EtOH	2.8 mL, 3:1 mixture	S-3 · Synthesis and Characterization of Ligands and dhMOF
Solvent	EtOH/H2O	2.8 mL, 1:1 mixture	S-3 · Synthesis and Characterization of Ligands and dhMOF
Solvent	EtOH	solvent exchange, 5 days for CO2-sorption activation	S-3 · Synthesis and Characterization of Ligands and dhMOF

Complete recipeSource: Both

Route 2: Other

S-4 · Iodine-Treated dhMOF (1a)

Linker precursorsEvacuated pristine dhMOF 1

AdditivesIodine chips

AtmosphereSealed larger screw-capped vial with parafilm; iodine vapour exposure; then open air overnight and vacuum

Temperatureambient

Time96 h iodine vapour exposure plus overnight open-air step

Oxidant / reductantI2 vapour oxidant; product contains I- counterions and ExTTFTB radical cations

Work-upMOF removed from outer iodine vial, left open overnight, kept under vacuum to remove excess physisorbed iodide from outer surface; main text also describes the analysed 1a as hexane-washed and evacuated.

ActivationStarting MOF was evacuated; final iodine-exposed material kept under vacuum.

Scalability context100 mg evacuated MOF charge used; gravimetric analysis showed ca. 9.5% mass increase.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	orange colored evacuated MOF	100 mg	S-4 · Iodine-Treated dhMOF (1a)
Oxidant	iodine chips / iodine vapor	a few iodine chips	S-4 · Iodine-Treated dhMOF (1a)

Partial recipeSource: Main

Route 3: Other

3 · Synthesis and Structural Characterization of ExTTFTB-Based dhMOF · Figure 2b

Linker precursorsPristine dhMOF 1

AdditivesIodine

AtmosphereIodine-treated then air-exposed; not washed

Temperatureambient

Oxidant / reductantIodine oxidant and residual iodine guest

Work-upAir exposed but not washed; retains additional iodine molecules according to TGA.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	pristine dhMOF 1	Not specified	3 · Synthesis and Structural Characterization of ExTTFTB-Based dhMOF · Figure 2b
Oxidant	iodine	Not specified	3 · Synthesis and Structural Characterization of ExTTFTB-Based dhMOF · Figure 2b

Complete recipeSource: Both

Route 4: Other

S-3 · Synthesis and Characterization of Ligands and dhMOF · Scheme S1

Linker precursorsExTTF core; ethyl 4-bromobenzoate; ExTTFTB-Et4 ester precursor

SolventsDry THF for Pd-catalysed coupling; 1:1 THF/MeOH plus H2O for saponification

AdditivesPd(AcO)2, tri-tert-butylphosphonium tetrafluoroborate, Cs(CO3)2, KOH, HCl

AtmosphereN2 environment for cross-coupling and saponification; degassed suspensions/solvents reported

Temperaturereflux

Time168 h coupling; 12 h saponification

Work-upCoupling: solvent removed, H2O/CH2Cl2 added, extracted organic layer, brine wash, Na2SO4 dry, evaporated, SiO2 column chromatography from 1:1 CH2Cl2/hexane to CH2Cl2. Saponification: solvent evaporated, 1 M HCl added, precipitate filtered, washed with H2O, air dried overnight.

ActivationExTTFTB-H4 further dried under high vacuum for 12 h

Scalability contextMain text describes the ligand as easily accessible and scalable; isolated yields were 83% for Et4ExTTFTB and 94% for ExTTFTB-H4.

Show 11 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	ExTTF	250 mg, 0.66 mmol	S-3 · Synthesis and Characterization of Ligands and dhMOF · Scheme S1
Other	ethyl 4-bromobenzoate	0.54 mL, 3.28 mmol	S-3 · Synthesis and Characterization of Ligands and dhMOF · Scheme S1
Additive	Pd(AcO)2	59 mg, 0.26 mmol	S-3 · Synthesis and Characterization of Ligands and dhMOF · Scheme S1
Additive	tri-tert-butylphosphonium tetrafluoroborate	230 mg, 0.79 mmol	S-3 · Synthesis and Characterization of Ligands and dhMOF · Scheme S1
Base	Cs(CO3)2	1.9 g, 5.94 mmol	S-3 · Synthesis and Characterization of Ligands and dhMOF · Scheme S1
Solvent	dry THF	6 mL + 20 mL	S-3 · Synthesis and Characterization of Ligands and dhMOF · Scheme S1
Other	ExTTFTB-Et4	304 mg, 0.31 mmol	S-3 · Synthesis and Characterization of Ligands and dhMOF · Scheme S1
Base	KOH	221 mg, 3.94 mmol	S-3 · Synthesis and Characterization of Ligands and dhMOF · Scheme S1
Solvent	1:1 THF/MeOH	12 mL	S-3 · Synthesis and Characterization of Ligands and dhMOF · Scheme S1
Solvent	distilled H2O	2 mL KOH solution; 50 mL wash	S-3 · Synthesis and Characterization of Ligands and dhMOF · Scheme S1
Acid	aqueous HCl	20 mL · 1 M	S-3 · Synthesis and Characterization of Ligands and dhMOF · Scheme S1

Complete recipeSource: SI

Route 5: Other

S-4 · Electrochemical Impedance and Electrical Conductivity Measurements on MOF Pellets · Figure S3a

Linker precursorsPristine or iodine-treated dhMOF powder

AdditivesConductive carbon ink or silver-coated stainless-steel rod tips

AtmosphereAmbient conditions for electrical measurements

Temperatureambient

Work-up2.5 mg MOF placed in Teflon tube, capped between two 2.7 mm stainless-steel rods with conductive carbon or silver-coated tips, then pressed under 200 MPa; pellet thickness ca. 0.2 mm.

Scalability contextSame pellet preparation used for pristine and iodine-treated MOF pellets for dc-sweep and ac impedance measurements.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	respective pristine or iodine-treated MOF material	2.5 mg	S-4 · Electrochemical Impedance and Electrical Conductivity Measurements on MOF Pellets · Figure S3a
Additive	conductive carbon ink or silver-coated tip	Not specified	S-4 · Electrochemical Impedance and Electrical Conductivity Measurements on MOF Pellets · Figure S3a
Other	Teflon tube	inner diameter 2.7 mm	S-4 · Electrochemical Impedance and Electrical Conductivity Measurements on MOF Pellets · Figure S3a
Other	stainless-steel rods	diameter 2.7 mm	S-4 · Electrochemical Impedance and Electrical Conductivity Measurements on MOF Pellets · Figure S3a