Synthesis · Redox-active conductive metal-organic framework with high lithium capacities at low temperatures

4 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

21733 · Synthesis of SKIER-5 · Figure 1a

Metal precursorsnickel acetate hexahydrate (Ni(OAc)2.6H2O)

Linker precursorsTATH

SolventsDMF; water and acetone washes

Additivesconcentrated aqueous ammonia

Atmosphereair

Temperature65-70

Timeovernight

Work-updark cyan precipitate separated by centrifugation, washed three times with water and acetone, dried under vacuum at 100 C overnight

Activationvacuum drying at 100 C overnight

Scalability contextReported isolated yield 180 mg, 30%.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel acetate hexahydrate (Ni(OAc)2.6H2O)	731.66 mg, 2.5 mmol	21733 · Synthesis of SKIER-5 · Figure 1a
Linker	TATH	380 mg, 0.637 mmol	21733 · Synthesis of SKIER-5 · Figure 1a
Solvent	DMF	10 mL for nickel solution plus 10 mL for TATH solution	21733 · Synthesis of SKIER-5 · Figure 1a
Base	concentrated aqueous ammonia	200 uL · concentrated	21733 · Synthesis of SKIER-5 · Figure 1a
Solvent	water and acetone	washed three times	21733 · Synthesis of SKIER-5 · Figure 1a

Complete recipeSource: SI

Route 2: Other

S2 · 2,3,9,10-TetraBromo intermediate synthesis · Figure S1

Linker precursors6,13-difluorobenzo[5,6][1,4]dithiino[2,3-b]thianthrene (1)

Solventsnitrobenzene; diethyl ether workup

Additivesiron powder

Atmospherenot specified

Temperature110

Timeovernight

Oxidant / reductantbromine

Work-upcooled to room temperature, mixed with diethyl ether, filtered; crude off-white solid used without characterisation

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	fluoro-thianthrene (1)	200 mg, 0.512 mmol	S2 · 2,3,9,10-TetraBromo intermediate synthesis · Figure S1
Solvent	nitrobenzene	10 mL	S2 · 2,3,9,10-TetraBromo intermediate synthesis · Figure S1
Additive	iron powder	10 mg, 0.184 mmol	S2 · 2,3,9,10-TetraBromo intermediate synthesis · Figure S1
Oxidant	bromine	158.6 uL, 3.07 mmol	S2 · 2,3,9,10-TetraBromo intermediate synthesis · Figure S1

Complete recipeSource: SI

Route 3: Other

S2 · Compound (3) · Figure S3

Metal precursorstris(dibenzylideneacetone)dipalladium(0)

Linker precursors2,3,9,10-tetrabromo-thianthrene 2; benzophenone imine

Solventstoluene; CH2Cl2 dilution; DCM/hexane chromatography

Additivesrac-BINAP; sodium tert-butoxide

Atmospheredegassed by freeze-pump-thaw and purged with Ar

Temperature110

Time0.5 h catalyst pre-stir, then overnight

Work-upcooled, diluted with CH2Cl2, filtered through Celite, rotary evaporated, purified by silica chromatography with DCM/hexane 1:2, dried

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	tris(dibenzylideneacetone)dipalladium(0)	609.67 mg, 0.66 mmol	S2 · Compound (3) · Figure S3
Additive	rac-BINAP	829.08 mg, 1.33 mmol	S2 · Compound (3) · Figure S3
Solvent	toluene	30 mL	S2 · Compound (3) · Figure S3
Linker	benzophenone imine	2.75 mL, 15.98 mmol	S2 · Compound (3) · Figure S3
Linker	2,3,9,10-tetrabromo-thianthrene 2	2 g, 2.66 mmol	S2 · Compound (3) · Figure S3
Base	sodium tert-butoxide	1.54 g, 15.98 mmol	S2 · Compound (3) · Figure S3

Complete recipeSource: Both

Route 4: Other

21733 · Synthesis of TATH · Figure S1

Linker precursorscompound 3

SolventsTHF; aqueous HCl; hexane wash

Additives2.0 M aqueous HCl

Atmospherenot specified

Temperatureroom temperature

Time0.5

Oxidant / reductantacid deprotection

Work-upprecipitate isolated by centrifugation, washed with hexane three times, dried under vacuum

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	compound 3	0.219 g, 0.17 mmol	21733 · Synthesis of TATH · Figure S1
Solvent	THF	10 mL	21733 · Synthesis of TATH · Figure S1
Acid	aqueous HCl	0.5 mL, 1.0 mmol · 2.0 M	21733 · Synthesis of TATH · Figure S1
Solvent	hexane	5.0 mL x 3	21733 · Synthesis of TATH · Figure S1