Synthesis · Structure–Property Engineering of Redox-Active Tetrathiafulvalene- and Bipyridine-Based Metal–Organic Frameworks for Battery Cathodes

7 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Drop Cast

11 · 4.2.6

Linker precursorsCd2(TTFTB) MOF powder

Solventsanhydrous NMP

AdditivesTOKABLACK #5500 conductive carbon; CMC binder

Atmospheredried under vacuum

Timeovernight drying

Substrate orientationAl foil, 20 um thickness

Work-upgrind active powder with carbon 40 min, add CMC and grind 40 min; doctor blade onto Al foil; vacuum dry overnight; cut 15.95 mm disks

Activationvacuum dry overnight

Scalability contextCR2032 cathode disks

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cd2(TTFTB) MOF or TTF-hybrid-MOF or H4TTFTB powder	30 wt%	11 · 4.2.6
Additive	TOKABLACK #5500	60 wt%	11 · 4.2.6
Additive	CMC	10 wt%	11 · 4.2.6
Solvent	anhydrous NMP	not specified	11 · 4.2.6

Complete recipeSource: Main

Route 2: Solvothermal

10 · 4.1.3

Metal precursorsCd(NO3)2.4H2O

Linker precursorsH4TTFTB

Solventswater/ethanol (1:1 v/v); DMF/ethanol (3:1 v/v)

Atmospherenot specified

Temperature75

Time78

Work-upcollect crystals by vacuum filtration; wash with DMF (30 mL) and ethanol (30 mL); dry under vacuum

Activationdried under vacuum

Scalability context38.6 mg product, 70% yield

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cd(NO3)2.4H2O	34.4 mg, 0.112 mmol	10 · 4.1.3
Linker	H4TTFTB	20.6 mg, 0.030 mmol	10 · 4.1.3
Solvent	water/ethanol	2.4 mL · 1:1 v/v	10 · 4.1.3
Solvent	DMF/ethanol	1.68 mL · 3:1 v/v	10 · 4.1.3

Complete recipeSource: Main

Route 3: Other

10 · 4.1.1

Linker precursorstetrathiafulvalene; ethyl 4-bromobenzoate

SolventsTHF; chloroform extraction; dichloromethane chromatography

AdditivesPd(OAc)2 catalyst; P(t-Bu)3.HBF4; Cs2CO3

Atmospherenitrogen

Temperature70

Time0.167 h pre-reflux plus 20 h reflux

Work-upcooled to RT; extracted three times with chloroform; organic layers washed with brine, dried over Na2SO4, concentrated; silica gel chromatography with dichloromethane

Scalability context1211.1 mg product, 1.59 mmol

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	palladium(II) acetate (Pd(OAc)2)	83.9 mg, 0.37 mmol	10 · 4.1.1
Additive	tri-tert-butylphosphonium tetrafluoroborate (P(But)3.HBF4)	325.9 mg, 1.12 mmol	10 · 4.1.1
Base	caesium carbonate (Cs2CO3)	2444.0 mg, 7.50 mmol	10 · 4.1.1
Solvent	tetrahydrofuran (THF)	15 mL + 15 mL	10 · 4.1.1
Linker	tetrathiafulvalene	307.6 mg, 1.51 mmol	10 · 4.1.1
Linker	ethyl 4-bromobenzoate	1718.0 mg, 7.5 mmol	10 · 4.1.1

Complete recipeSource: Main

Route 4: Other

10 · 4.1.2

Linker precursorsEt4TTFTB

Solventsmethanol; THF; purified water

AdditivesKOH; HCl

Atmospherenitrogen; degassed solvents

Temperature70

Time20

Work-upcool to RT; remove volatiles under reduced pressure; add 1 M HCl; collect maroon precipitate by suction filtration; wash with water; dry under high vacuum for 12 h

Activationhigh vacuum dry 12 h

Scalability context849.6 mg, 1.241 mmol H4TTFTB obtained

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	Et4TTFTB	1211.1 mg, 1.59 mmol	10 · 4.1.2
Solvent	methanol	20 mL	10 · 4.1.2
Solvent	THF	20 mL	10 · 4.1.2
Base	KOH	1074.2 mg, 19.14 mmol	10 · 4.1.2
Solvent	purified water	20 mL for KOH; 50 mL wash · 15.0 Mohm cm resistivity	10 · 4.1.2
Acid	HCl	10 mL · 1 M	10 · 4.1.2

Complete recipeSource: Main

Route 5: Drop Cast

11 · 4.2.6

Linker precursorsH4TTFTB powder

Solventsanhydrous NMP

AdditivesTOKABLACK #5500 conductive carbon; CMC binder

Atmospheredried under vacuum

Timeovernight drying

Substrate orientationAl foil, 20 um thickness

Work-upgrind active powder with carbon 40 min, add CMC and grind 40 min; doctor blade onto Al foil; vacuum dry overnight; cut 15.95 mm disks

Activationvacuum dry overnight

Scalability contextCR2032 cathode disks

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	H4TTFTB powder	30 wt%	11 · 4.2.6
Additive	TOKABLACK #5500	60 wt%	11 · 4.2.6
Additive	CMC	10 wt%	11 · 4.2.6
Solvent	anhydrous NMP	not specified	11 · 4.2.6

Complete recipeSource: Main

Route 6: Drop Cast

11 · 4.2.6

Linker precursorsTTF-hybrid-MOF powder

Solventsanhydrous NMP

AdditivesTOKABLACK #5500 conductive carbon; CMC binder

Atmospheredried under vacuum

Timeovernight drying

Substrate orientationAl foil, 20 um thickness

Work-upgrind active powder with carbon 40 min, add CMC and grind 40 min; doctor blade onto Al foil; vacuum dry overnight; cut 15.95 mm disks

Activationvacuum dry overnight

Scalability contextCR2032 cathode disks

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	TTF-hybrid-MOF powder	30 wt%	11 · 4.2.6
Additive	TOKABLACK #5500	60 wt%	11 · 4.2.6
Additive	CMC	10 wt%	11 · 4.2.6
Solvent	anhydrous NMP	not specified	11 · 4.2.6

Complete recipeSource: Main

Route 7: Solvothermal

10-11 · 4.1.4/4.2.5

Metal precursorsCdCl2.2.5H2O

Linker precursorsH4TTFTB; 1,2-bis(4-pyridyl)ethane

Solventsethanol; water; DMF/ethanol (3:1 v/v)

Atmospherenot specified

Temperature75

Time78

Work-upvacuum filtration; wash with DMF (30 mL) and ethanol (30 mL); dry under vacuum

Activationdried under vacuum; for gas adsorption, DCM solvent exchange for approximately 3 days then vacuum filtration and drying

Scalability context49.1 mg product, 32% yield

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CdCl2.2.5H2O	46 mg, 0.201 mmol	10-11 · 4.1.4/4.2.5
Linker	1,2-bis(4-pyridyl)ethane	37 mg, 0.201 mmol	10-11 · 4.1.4/4.2.5
Linker	H4TTFTB	69 mg, 0.101 mmol	10-11 · 4.1.4/4.2.5
Solvent	ethanol	10 mL plus DMF/ethanol mixture	10-11 · 4.1.4/4.2.5
Solvent	water	10 mL	10-11 · 4.1.4/4.2.5
Solvent	DMF/ethanol	10 mL · 3:1 v/v	10-11 · 4.1.4/4.2.5
Solvent	dichloromethane (DCM)	2 mL for 94.4 mg powder · solvent exchange for ca. 3 days	10-11 · 4.1.4/4.2.5