Synthesis · Redox-Active Metal-Organic Frameworks with Three-Dimensional Lattice Containing the m-Tetrathiafulvalene-Tetrabenzoate

5 structured synthesis routes

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

Vague recipeSource: Main

Route 1: Unknown

8 · 3.4 Synthesis of Dy-m-TTFTB

Metal precursorsnot provided; prepared according to reported method [33]

Linker precursorsnot provided in this paper; m-TTFTB framework implied

Solventsnot provided

Additivesnot provided

Atmospherenot provided

Work-upnot provided

Activationnot provided

Complete recipeSource: Main

Route 2: Solvothermal

8-9 · 3.6 Synthesis of Er-m-TTFTB

Metal precursorsErCl3.6H2O (0.010 g, ~0.027 mmol)

Linker precursorsm-H4TTFTB (0.010 g, 0.015 mmol; same conditions as Tb route)

SolventsDMF (1 mL), H2O (0.5 mL), chlorobenzene (2 mL); same conditions as Tb route

AdditivesCF3COOH (0.17 mL); same conditions as Tb route

Atmospherenot specified

Temperature140

Time48

Oxidant / reductantnone specified

Work-upred rod-like crystals filtered and washed with DMF and acetone three times

Activationnone reported

Scalability context0.010 g crystals; 60% yield based on m-H4TTFTB.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	m-H4TTFTB	0.010 g, 0.015 mmol (same as Tb route)	8-9 · 3.6 Synthesis of Er-m-TTFTB
Metal Source	ErCl3.6H2O	0.010 g, ~0.027 mmol	8-9 · 3.6 Synthesis of Er-m-TTFTB
Solvent	DMF	1 mL (same as Tb route)	8-9 · 3.6 Synthesis of Er-m-TTFTB
Solvent	H2O	0.5 mL (same as Tb route)	8-9 · 3.6 Synthesis of Er-m-TTFTB
Acid	CF3COOH	0.17 mL (same as Tb route)	8-9 · 3.6 Synthesis of Er-m-TTFTB
Solvent	chlorobenzene	2 mL (same as Tb route)	8-9 · 3.6 Synthesis of Er-m-TTFTB

Partial recipeSource: Main

Route 3: Solvothermal

9 · 3.7 Synthesis of Gd-m-TTFTB

Metal precursorsnot explicitly stated in available text; expected Gd chloride by analogy but not normalised here

Linker precursorsnot explicitly restated; likely m-H4TTFTB by series context

Solventsnot explicitly restated; likely same as Tb/Er conditions by series context

Additivesnot explicitly restated

Atmospherenot specified

Oxidant / reductantnone specified

Work-upred rod-like crystals filtered and washed with DMF and acetone three times

Activationnone reported

Scalability context0.008 g crystals; 48% yield based on m-H4TTFTB.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	m-H4TTFTB	not explicitly restated; yield based on m-H4TTFTB	9 · 3.7 Synthesis of Gd-m-TTFTB
Metal Source	Gd source not explicitly stated in text layer	Not specified	9 · 3.7 Synthesis of Gd-m-TTFTB
Solvent	DMF	wash solvent; reaction solvent not explicitly restated	9 · 3.7 Synthesis of Gd-m-TTFTB
Solvent	CH3COCH3	wash solvent	9 · 3.7 Synthesis of Gd-m-TTFTB

Complete recipeSource: SI

Route 4: Other

14 · Figure S19 ligand synthesis · Figure S19

Metal precursorsnone

Linker precursorstetrathiafulvalene; ethyl m-bromobenzoate via Pd-catalysed coupling to m-Et4-TTFTB, then KOH hydrolysis/acidification

Solventsdegassed THF; dichloromethane extraction; petroleum ether/DCM (1:3) chromatography; THF/MeOH/H2O for hydrolysis

AdditivesPd(OAc)2; P(t-Bu)3HBF4; Cs2CO3; KOH; HCl

Atmospherenitrogen for coupling step; air for hydrolysis step

Temperature60 deg C preheat; THF reflux 72 h; 90 deg C overnight hydrolysis

Time0.5 h pre-stir; 72 h reflux; overnight hydrolysis

Oxidant / reductantnone specified

Work-upconcentrated in vacuo; DCM extraction/filtration; silica chromatography; concentrated; water dissolution; HCl to pH 2; centrifugation; water washing; vacuum drying

Activationvacuum drying

Scalability contextLigand isolated on gram scale: 3.22 g final acid, 81% hydrolysis yield; ester intermediate 2.2 g, 37.6%.

Show 10 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	Pd(OAc)2	410 mg, 1.83 mmol	14 · Figure S19 ligand synthesis · Figure S19
Additive	P(t-Bu)3HBF4	1.60 g, 5.51 mmol	14 · Figure S19 ligand synthesis · Figure S19
Base	Cs2CO3	12 g, 36.83 mmol	14 · Figure S19 ligand synthesis · Figure S19
Solvent	degassed THF	100 mL	14 · Figure S19 ligand synthesis · Figure S19
Linker	tetrathiafulvalene	1.5 g, 7.34 mmol	14 · Figure S19 ligand synthesis · Figure S19
Other	ethyl m-bromobenzoate	9.47 g, 41.34 mmol	14 · Figure S19 ligand synthesis · Figure S19
Other	m-Et4-TTFTB	4.10 g, 5.14 mmol	14 · Figure S19 ligand synthesis · Figure S19
Solvent	THF/MeOH	150 mL/150 mL	14 · Figure S19 ligand synthesis · Figure S19
Base	KOH	4.0 g, 71.28 mmol in 30 mL water	14 · Figure S19 ligand synthesis · Figure S19
Acid	HCl	to pH 2	14 · Figure S19 ligand synthesis · Figure S19

Complete recipeSource: Main

Route 5: Solvothermal

8 · 3.5 Synthesis of Tb-m-TTFTB

Metal precursorsTbCl3.6H2O (0.010 g, ~0.027 mmol)

Linker precursorsm-H4TTFTB (0.010 g, 0.015 mmol)

SolventsDMF (1 mL), H2O (0.5 mL), chlorobenzene (2 mL)

AdditivesCF3COOH (0.17 mL)

Atmospherenot specified

Temperature140

Time48

Oxidant / reductantnone specified

Work-upcooled to room temperature; red rod-like crystals filtered and washed with DMF and acetone three times

Activationnone reported

Scalability context0.009 g crystals; 54% yield based on m-H4TTFTB.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	m-H4TTFTB	0.010 g, 0.015 mmol	8 · 3.5 Synthesis of Tb-m-TTFTB
Metal Source	TbCl3.6H2O	0.010 g, ~0.027 mmol	8 · 3.5 Synthesis of Tb-m-TTFTB
Solvent	DMF	1 mL	8 · 3.5 Synthesis of Tb-m-TTFTB
Solvent	H2O	0.5 mL	8 · 3.5 Synthesis of Tb-m-TTFTB
Acid	CF3COOH	0.17 mL	8 · 3.5 Synthesis of Tb-m-TTFTB
Solvent	chlorobenzene	2 mL	8 · 3.5 Synthesis of Tb-m-TTFTB