Synthesis · High performance Li-, Na-, and K-ion storage in electrically conducting coordination polymers

7 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

p004 / SI p.4 · 1.2 Synthesis of H4-PTtSA

Linker precursors1,2,4,5-benzenetetramine tetrahydrochloride, 2.48 g, 0.01 mol

Solventspyridine, 50 mL; 1 M HCl solution, 200 mL; water wash

Additivesmethanesulfonyl chloride, 3.25 mL, 42 mmol

Temperature0 C addition, then room temperature; vacuum drying at 70 C

Time0.5 h dropwise addition; 24 h stirring

Work-upAdded 200 mL 1 M HCl, precipitate washed with large amount of 1 M HCl and water.

ActivationDried under vacuum at 70 C.

Scalability contextGram-scale precursor recipe reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1,2,4,5-Benzenetetramine tetrahydrochloride	2.48 g, 0.01 mol	p004 / SI p.4 · 1.2 Synthesis of H4-PTtSA
Solvent	pyridine	50 ml	p004 / SI p.4 · 1.2 Synthesis of H4-PTtSA
Additive	methanesulfonyl chloride	3.25 ml, 42 mmol	p004 / SI p.4 · 1.2 Synthesis of H4-PTtSA
Acid	HCl solution	200 ml · 1 M	p004 / SI p.4 · 1.2 Synthesis of H4-PTtSA
Solvent	water	wash solvent	p004 / SI p.4 · 1.2 Synthesis of H4-PTtSA

Complete recipeSource: Both

Route 2: Other

p005 / SI p.5 · 1.7 Synthesis of K2-Co-PTtSA

Metal precursorsanhydrous cobalt(II) chloride, 65 mg, 0.5 mmol

Linker precursorsH4-PTtSA, 225 mg, 0.5 mmol; deprotonated in situ to K4-PTtSA

Solventsanhydrous methanol, 5 mL plus 3 mL; methanol and diethyl ether washes

Additivespotassium methoxide, 140 mg, 2 mmol

Atmosphereinert atmosphere

Temperatureroom temperature reaction; 60 C and 180 C drying

Time48 h stirring; 2 h at 60 C; 4 h at 180 C

Work-upFiltered, washed with methanol and diethyl ether.

ActivationDried at 60 C for 2 h, then at 180 C for 4 h.

Scalability context0.5 mmol batch scale reported; no scale-up study.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H4-PTtSA	225 mg, 0.5 mmol	p005 / SI p.5 · 1.7 Synthesis of K2-Co-PTtSA
Base	potassium methoxide	140 mg, 2 mmol	p005 / SI p.5 · 1.7 Synthesis of K2-Co-PTtSA
Metal Source	anhydrous cobalt (II) chloride	65 mg, 0.5 mmol	p005 / SI p.5 · 1.7 Synthesis of K2-Co-PTtSA
Solvent	anhydrous methanol	5 ml + 3 ml	p005 / SI p.5 · 1.7 Synthesis of K2-Co-PTtSA

Complete recipeSource: Both

Route 3: Other

p004 / SI p.4 · 1.3 Synthesis of Li2-Co-PTtSA

Metal precursorsanhydrous cobalt(II) chloride, 65 mg, 0.5 mmol

Linker precursorsH4-PTtSA, 225 mg, 0.5 mmol; deprotonated in situ to Li4-PTtSA

Solventsanhydrous methanol, 5 mL for ligand/base solution plus 3 mL for CoCl2 solution; methanol and diethyl ether washes

Additiveslithium methoxide, 76 mg, 2 mmol

Atmosphereinert atmosphere

Temperatureroom temperature reaction; 60 C and 180 C drying

Time48 h stirring; 2 h at 60 C; 4 h at 180 C

Work-upFiltered, washed with methanol and diethyl ether.

ActivationDried at 60 C for 2 h, then at 180 C for 4 h.

Scalability context0.5 mmol batch scale reported; no scale-up study.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H4-PTtSA	225 mg, 0.5 mmol	p004 / SI p.4 · 1.3 Synthesis of Li2-Co-PTtSA
Base	lithium methoxide	76 mg, 2 mmol	p004 / SI p.4 · 1.3 Synthesis of Li2-Co-PTtSA
Metal Source	anhydrous cobalt (II) chloride	65 mg, 0.5 mmol	p004 / SI p.4 · 1.3 Synthesis of Li2-Co-PTtSA
Solvent	anhydrous methanol	5 ml + 3 ml	p004 / SI p.4 · 1.3 Synthesis of Li2-Co-PTtSA
Solvent	diethyl ether	wash solvent	p004 / SI p.4 · 1.3 Synthesis of Li2-Co-PTtSA

Complete recipeSource: Both

Route 4: Other

p004 / SI p.4 · 1.4 Synthesis of Li2-Fe-PTtSA

Metal precursorsanhydrous iron(II) chloride, 63.4 mg, 0.5 mmol

Linker precursorsH4-PTtSA, 225 mg, 0.5 mmol; deprotonated in situ to Li4-PTtSA

Solventsanhydrous methanol, 5 mL plus 3 mL; methanol and diethyl ether washes

Additiveslithium methoxide, 76 mg, 2 mmol

Atmosphereinert atmosphere

Temperatureroom temperature reaction; 60 C and 180 C drying

Time48 h stirring; 2 h at 60 C; 4 h at 180 C

Work-upFiltered, washed with methanol and diethyl ether.

ActivationDried at 60 C for 2 h, then at 180 C for 4 h.

Scalability context0.5 mmol batch scale reported; no scale-up study.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H4-PTtSA	225 mg, 0.5 mmol	p004 / SI p.4 · 1.4 Synthesis of Li2-Fe-PTtSA
Base	lithium methoxide	76 mg, 2 mmol	p004 / SI p.4 · 1.4 Synthesis of Li2-Fe-PTtSA
Metal Source	anhydrous iron (II) chloride	63.4 mg, 0.5 mmol	p004 / SI p.4 · 1.4 Synthesis of Li2-Fe-PTtSA
Solvent	anhydrous methanol	5 ml + 3 ml	p004 / SI p.4 · 1.4 Synthesis of Li2-Fe-PTtSA

Complete recipeSource: Both

Route 5: Other

p005 / SI p.5 · 1.5 Synthesis of Li2-Mn-PTtSA

Metal precursorsanhydrous manganese(II) chloride, 62.9 mg, 0.5 mmol

Linker precursorsH4-PTtSA, 225 mg, 0.5 mmol; deprotonated in situ to Li4-PTtSA

Solventsanhydrous methanol, 5 mL plus 3 mL; methanol and diethyl ether washes

Additiveslithium methoxide, 76 mg, 2 mmol

Atmosphereinert atmosphere

Temperatureroom temperature reaction; 60 C and 180 C drying

Time48 h stirring; 2 h at 60 C; 4 h at 180 C

Work-upFiltered, washed with methanol and diethyl ether.

ActivationDried at 60 C for 2 h, then at 180 C for 4 h.

Scalability context0.5 mmol batch scale reported; no scale-up study.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H4-PTtSA	225 mg, 0.5 mmol	p005 / SI p.5 · 1.5 Synthesis of Li2-Mn-PTtSA
Base	lithium methoxide	76 mg, 2 mmol	p005 / SI p.5 · 1.5 Synthesis of Li2-Mn-PTtSA
Metal Source	anhydrous manganese (II) chloride	62.9 mg, 0.5 mmol	p005 / SI p.5 · 1.5 Synthesis of Li2-Mn-PTtSA
Solvent	anhydrous methanol	5 ml + 3 ml	p005 / SI p.5 · 1.5 Synthesis of Li2-Mn-PTtSA

Complete recipeSource: SI

Route 6: Other

p005 / SI p.5 · 1.8 Synthesis of Li2-o-Co-PTtSA

Metal precursorsanhydrous cobalt(II) chloride, 65 mg, 0.5 mmol

Linker precursorsH2-o-PDSA, 264 mg, 1 mmol; deprotonated in situ to Li2-o-PDSA

Solventsanhydrous methanol, 5 mL plus 3 mL; diethyl ether added and used for diffusion crystallisation

Additiveslithium methoxide, 76 mg, 2 mmol

Atmosphereinert atmosphere

Temperatureroom temperature

Time48 h stirring

Work-upLarge amount of diethyl ether added; precipitate filtered and washed with diethyl ether three times.

ActivationSingle crystal prepared by diffusion of diethyl ether into methanol solution.

Scalability contextModel complex synthesis only; not a scalable CP route.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H2-o-PDSA	264 mg, 1 mmol	p005 / SI p.5 · 1.8 Synthesis of Li2-o-Co-PTtSA
Base	lithium methoxide	76 mg, 2 mmol	p005 / SI p.5 · 1.8 Synthesis of Li2-o-Co-PTtSA
Metal Source	anhydrous cobalt (II) chloride	65 mg, 0.5 mmol	p005 / SI p.5 · 1.8 Synthesis of Li2-o-Co-PTtSA
Solvent	anhydrous methanol	5 ml + 3 ml	p005 / SI p.5 · 1.8 Synthesis of Li2-o-Co-PTtSA
Solvent	diethyl ether	large amount; wash and diffusion solvent	p005 / SI p.5 · 1.8 Synthesis of Li2-o-Co-PTtSA

Complete recipeSource: Both

Route 7: Other

p005 / SI p.5 · 1.6 Synthesis of Na2-Co-PTtSA

Metal precursorsanhydrous cobalt(II) chloride, 65 mg, 0.5 mmol

Linker precursorsH4-PTtSA, 225 mg, 0.5 mmol; deprotonated in situ to Na4-PTtSA

Solventsanhydrous methanol, 5 mL plus 3 mL; methanol and diethyl ether washes

Additivessodium methoxide, 108 mg, 2 mmol

Atmosphereinert atmosphere

Temperatureroom temperature reaction; 60 C and 180 C drying

Time48 h stirring; 2 h at 60 C; 4 h at 180 C

Work-upFiltered, washed with methanol and diethyl ether.

ActivationDried at 60 C for 2 h, then at 180 C for 4 h.

Scalability context0.5 mmol batch scale reported; no scale-up study.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H4-PTtSA	225 mg, 0.5 mmol	p005 / SI p.5 · 1.6 Synthesis of Na2-Co-PTtSA
Base	sodium methoxide	108 mg, 2 mmol	p005 / SI p.5 · 1.6 Synthesis of Na2-Co-PTtSA
Metal Source	anhydrous cobalt (II) chloride	65 mg, 0.5 mmol	p005 / SI p.5 · 1.6 Synthesis of Na2-Co-PTtSA
Solvent	anhydrous methanol	5 ml + 3 ml	p005 / SI p.5 · 1.6 Synthesis of Na2-Co-PTtSA