Synthesis · High charge mobility in a tetrathiafulvalene-based microporous metal-organic framework

3 structured synthesis routes

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

Partial recipeSource: Both

Route 1: Other

SI p.S2-S3 · Tetrathiafulvalene tetrabenzoic acid . 1.5 CH3OH · Scheme 1 in main article

Metal precursorsNone.

Linker precursorsEt4TTFTB, itself prepared according to a literature procedure; Scheme 1 shows cross-coupling of TTF with ethyl-4-bromobenzoate before hydrolysis.

SolventsDegassed methanol (7 mL), THF (7 mL), distilled water (5 mL); Scheme 1 also lists CH3OH/H2O/THF for hydrolysis.

AdditivesSodium hydroxide; hydrochloric acid workup. Scheme 1 first step lists Cs2CO3, Pd(OAc)2 and HPtBu3(BF4) in THF.

AtmosphereMethanol, THF and water degassed with nitrogen for 30 min; flask subjected to three evacuation/N2 refill cycles; addition under N2.

Temperaturereflux

Time12

Oxidant / reductantNo oxidant/reductant for the reported saponification; Pd-catalysed cross-coupling step shown in Scheme 1 but not detailed in SI.

Work-upCooled to room temperature; volatiles removed in vacuo; 1 M HCl (30 mL) added; maroon precipitate filtered, washed with water (50 mL), dried under high vacuum 12 h.

ActivationDried under high vacuum for 12 h.

Scalability contextSI scale: 734 mg Et4TTFTB gave 556.5 mg H4TTFTB, 88% yield. Full Et4TTFTB precursor synthesis is cited to literature rather than detailed.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	Et4TTFTB	734 mg, 0.921 mmol	SI p.S2-S3 · Tetrathiafulvalene tetrabenzoic acid . 1.5 CH3OH · Scheme 1 in main article
Base	sodium hydroxide	466 mg, 11.6 mmol	SI p.S2-S3 · Tetrathiafulvalene tetrabenzoic acid . 1.5 CH3OH · Scheme 1 in main article
Acid	HCl solution	30 mL · 1 M	SI p.S2-S3 · Tetrathiafulvalene tetrabenzoic acid . 1.5 CH3OH · Scheme 1 in main article
Solvent	degassed methanol	7 mL	SI p.S2-S3 · Tetrathiafulvalene tetrabenzoic acid . 1.5 CH3OH · Scheme 1 in main article
Solvent	degassed THF	7 mL	SI p.S2-S3 · Tetrathiafulvalene tetrabenzoic acid . 1.5 CH3OH · Scheme 1 in main article
Solvent	degassed distilled water	5 mL for NaOH solution plus 50 mL wash	SI p.S2-S3 · Tetrathiafulvalene tetrabenzoic acid . 1.5 CH3OH · Scheme 1 in main article
Other	TTF and ethyl-4-bromobenzoate; Cs2CO3, Pd(OAc)2, HPtBu3(BF4) in THF	shown in main Scheme 1 without quantities	SI p.S2-S3 · Tetrathiafulvalene tetrabenzoic acid . 1.5 CH3OH · Scheme 1 in main article

Complete recipeSource: Both

Route 2: Solvothermal

SI p.S3 · Bulk synthesis

Metal precursorsZinc nitrate hexahydrate, 319 mg, 1.07 mmol, dissolved in 1:1 water/ethanol (32 mL).

Linker precursorsH4TTFTB, 200 mg, 0.292 mmol, dissolved in DMF (24 mL) with ethanol (8 mL).

SolventsWater/ethanol 1:1 (32 mL) for metal solution; DMF (24 mL) plus ethanol (8 mL) for linker solution.

AdditivesNone reported.

AtmosphereNot reported for MOF synthesis; activation under vacuum.

Temperature75

Time72

Oxidant / reductantNone intentionally added; EPR indicates partial oxidation occurs during MOF synthesis.

Work-upZinc nitrate solution slowly added to H4TTFTB solution while avoiding precipitation; heated to afford precipitate; collected by filtration and washed with DMF (40 mL) and ethanol (40 mL).

ActivationPowder evacuated at 200 deg C for 12 h at 4 mTorr; SI gas-sorption method used 200 deg C under 2 mtorr vacuum for 12 h until outgas rate <2 mtorr/min.

Scalability contextBulk route gave 221 mg dark maroon powder, 0.218 mmol, 75% yield.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	zinc nitrate hexahydrate	319 mg, 1.07 mmol · dissolved in 1:1 water/ethanol (32 mL)	SI p.S3 · Bulk synthesis
Linker	H4TTFTB	200 mg, 0.292 mmol · dissolved in DMF (24 mL), then ethanol (8 mL) added	SI p.S3 · Bulk synthesis
Solvent	water/ethanol	32 mL · 1:1	SI p.S3 · Bulk synthesis
Solvent	DMF	24 mL	SI p.S3 · Bulk synthesis
Solvent	ethanol	8 mL plus ethanol in 1:1 water/ethanol solution; 40 mL wash	SI p.S3 · Bulk synthesis
Solvent	DMF wash	40 mL	SI p.S3 · Bulk synthesis

Complete recipeSource: SI

Route 3: Solvothermal

SI p.S3 · Zn2TTFTB(H2O)3(DMF)2 (1). X-ray quality single crystals

Metal precursorsZinc nitrate hexahydrate solution in 1:1 water/ethanol, 66.5 mM, 0.7 mL.

Linker precursorsH4TTFTB solution in 3:1 DMF/ethanol, 17.9 mM, 0.7 mL.

Solvents1:1 water/ethanol for zinc solution; 3:1 DMF/ethanol for ligand solution.

AdditivesNone reported.

AtmosphereNot reported.

Temperature65

Time72

Oxidant / reductantNone intentionally added; product is intrinsically partially oxidised according to EPR discussion.

Work-upDark red needles obtained; isolation workup for single crystals not further reported.

ActivationNo activation before single-crystal XRD; solvent/water present in formula.

Scalability contextSmall-volume route for X-ray-quality single crystals; no yield reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	zinc nitrate hexahydrate	0.7 mL solution · 66.5 mM in 1:1 water/ethanol	SI p.S3 · Zn2TTFTB(H2O)3(DMF)2 (1). X-ray quality single crystals
Linker	H4TTFTB	0.7 mL solution · 17.9 mM in 3:1 DMF/ethanol	SI p.S3 · Zn2TTFTB(H2O)3(DMF)2 (1). X-ray quality single crystals
Solvent	water/ethanol	0.7 mL metal solution · 1:1	SI p.S3 · Zn2TTFTB(H2O)3(DMF)2 (1). X-ray quality single crystals
Solvent	DMF/ethanol	0.7 mL linker solution · 3:1	SI p.S3 · Zn2TTFTB(H2O)3(DMF)2 (1). X-ray quality single crystals