Synthesis · Mixed Ionic and Electronic Conductivity in a Tetrathiafulvalene-Phosphonate Metal-Organic Framework

3 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Other

S5 · Synthesis of H8TTFTP · Scheme S1

Linker precursorstetrathiafulvalene; diethyl (4-bromophenyl)phosphonate

Solventsdistilled THF; CH2Cl2/H2O extraction; CH2Cl2 and CH2Cl2/MeOH (94:6) chromatography; CH2Cl2/hexane crystallisation

AdditivesPd(OAc)2; PtBu3·HBF4; Cs2CO3

Atmospherenitrogen/inert N2; away from sunlight

Temperature40 °C pre-stir; 80 °C reaction

Time0.167 h pre-stir; 48 h reaction

Work-upSolvent evaporated; residue extracted with CH2Cl2/H2O; aqueous layer washed with CH2Cl2; organic layer dried with MgSO4; solvent evaporated; silica-gel chromatography; crystallisation.

Scalability context50 mL flask scale; 1.09 g product, 70% yield.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	tetrathiafulvalene	302 mg, 1.48 mmol	S5 · Synthesis of H8TTFTP · Scheme S1
Linker	diethyl (4-bromophenyl)phosphonate	2.257 g, 7.70 mmol	S5 · Synthesis of H8TTFTP · Scheme S1
Additive	Pd(OAc)2	88 mg, 0.39 mmol	S5 · Synthesis of H8TTFTP · Scheme S1
Additive	PtBu3·HBF4	326 mg, 1.12 mmol	S5 · Synthesis of H8TTFTP · Scheme S1
Base	Cs2CO3	2.425 g, 7.44 mmol	S5 · Synthesis of H8TTFTP · Scheme S1
Solvent	distilled THF	5 mL + 10.0 mL	S5 · Synthesis of H8TTFTP · Scheme S1

Complete recipeSource: SI

Route 2: Other

S9 · Synthesis of H8TTFTP · Scheme S2

Linker precursorsEt8TTFTP

Solventsdry CH2Cl2; MeOH/H2O (1:1); H2O wash

Additivesbromotrimethylsilane

Atmospherecovered from sunlight; atmosphere not otherwise specified

Temperature30

Time24 h, followed by precipitation after MeOH/H2O addition

Work-upMeOH/H2O added; dark precipitate formed; washed by centrifugation several times with H2O.

Scalability context501.3 mg Et8TTFTP input; 370 mg H8TTFTP product, 94% yield.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	Et8TTFTP	501.3 mg, 0.476 mmol	S9 · Synthesis of H8TTFTP · Scheme S2
Additive	bromotrimethylsilane	1.16 mL, 12.124 mmol	S9 · Synthesis of H8TTFTP · Scheme S2
Solvent	dry CH2Cl2	5 mL	S9 · Synthesis of H8TTFTP · Scheme S2
Solvent	MeOH/H2O	10 mL · 1:1	S9 · Synthesis of H8TTFTP · Scheme S2

Complete recipeSource: Both

Route 3: Solvothermal

S12 · Synthesis of TTFTP-La MOF · Scheme S3

Metal precursorsLa2O3

Linker precursorsH8TTFTP

Solventswater/ethanol (1:1)

AdditivesHCl (6 M)

Atmospheresealed autoclave; atmosphere not specified

Temperature160

Time48

Work-upStirred 10 min at room temperature; after cooling, dark crystals filtered under vacuum and washed several times with water and ethanol.

ActivationAs-synthesised route has no activation step. Gas-sorption sample was heated/degassed at 150 °C under vacuum (main: 12 h; SI: overnight at 10^-6 Torr).

Scalability contextSmall autoclave batch: 22.2 mg product, 46% yield.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H8TTFTP	41.4 mg, 0.050 mmol	S12 · Synthesis of TTFTP-La MOF · Scheme S3
Metal Source	lanthanum oxide	48.9 mg, 0.1501 mmol	S12 · Synthesis of TTFTP-La MOF · Scheme S3
Acid	HCl	2.0 mL · 6 M	S12 · Synthesis of TTFTP-La MOF · Scheme S3
Solvent	water and ethanol	6 mL · 1:1	S12 · Synthesis of TTFTP-La MOF · Scheme S3