Synthesis · Conductive metal-organic frameworks with wheel-shaped metallomacrocycle subunits as high-performance supercapacitor electrodes

4 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Solvothermal

3 · Section 2.4.1

Metal precursorsCoCl2.6H2O (1.5 mmol, 0.36 g)

Linker precursorsH2mba (3 mmol, 0.46 g)

Solventsanhydrous ethanol (10 mL); deionised water (5 mL for cobalt salt)

AdditivesNaOH (3 mmol, 0.12 g); dilute HCl used in workup

Atmospheresealed Teflon-lined stainless-steel reactor; atmosphere not specified

Temperature120

Time96

Oxidant / reductanthydrothermal/solvothermal oxidation of thiosalicylic acid ligands to Hdtba described in structure discussion

Work-upcool to 25 C; wash several times with dilute hydrochloric acid, deionised water and anhydrous ethanol sequentially

Activationdried in an electric blast oven at 90 C

Scalability context0.38 g product, 46.40 wt% yield based on CoCl2.6H2O and H2mba

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Base	sodium hydroxide	3 mmol, 0.12 g	3 · Section 2.4.1
Solvent	anhydrous ethanol	10 mL	3 · Section 2.4.1
Linker	H2mba	3 mmol, 0.46 g	3 · Section 2.4.1
Metal Source	CoCl2.6H2O	1.5 mmol, 0.36 g	3 · Section 2.4.1
Solvent	deionised water	5 mL	3 · Section 2.4.1
Acid	dilute hydrochloric acid	wash · dilute	3 · Section 2.4.1

Complete recipeSource: Main

Route 2: Solvothermal

3 · Section 2.4.2

Metal precursorsCoCl2.6H2O (0.75 mmol, 0.18 g); NiCl2.6H2O (1.50 mmol, 0.36 g)

Linker precursorsH2mba (3 mmol, 0.46 g)

Solventsanhydrous ethanol (10 mL); deionised water (5 mL for metal salts)

AdditivesNaOH (3 mmol, 0.12 g); hydrochloric acid used in workup

Atmospheresealed Teflon-lined stainless-steel reactor; atmosphere not specified

Temperature120

Time96

Oxidant / reductanthydrothermal/solvothermal conditions oxidise some Co/Ni nodes to trivalent states; Hdtba formed by oxidation of two thiosalicylic acid ligands

Work-upcool to 27 C; wash several times with hydrochloric acid, deionised water and anhydrous ethanol in order

Activationdried in an electric blast oven at 100 C

Scalability context0.45 g product, 45.10 wt% yield based on NiCl2.6H2O, CoCl2.6H2O and H2mba

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Base	sodium hydroxide	3 mmol, 0.12 g	3 · Section 2.4.2
Solvent	anhydrous ethanol	10 mL	3 · Section 2.4.2
Linker	H2mba	3 mmol, 0.46 g	3 · Section 2.4.2
Metal Source	CoCl2.6H2O	0.75 mmol, 0.18 g	3 · Section 2.4.2
Metal Source	NiCl2.6H2O	1.50 mmol, 0.36 g	3 · Section 2.4.2
Solvent	deionised water	5 mL	3 · Section 2.4.2
Acid	hydrochloric acid	wash · not specified	3 · Section 2.4.2

Partial recipeSource: Main

Route 3: Solvothermal

3 · Section 2.4.3

Metal precursorsCoCl2.6H2O and NiCl2.6H2O with Co:Ni molar ratios 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 2:3, 2:5, 3:1, 3:2, 3:4, 3:5 and 4:5

Linker precursorsH2mba, same method as MWM-1(Co/2Ni)

Solventsanhydrous ethanol and deionised water, same method as MWM-1(Co/2Ni)

AdditivesNaOH; hydrochloric acid workup, same method as MWM-1(Co/2Ni)

Atmospheresealed Teflon-lined reactor; atmosphere not specified

Temperature120

Time96

Oxidant / reductantsame as MWM-1(Co/2Ni)

Work-upsame as MWM-1(Co/2Ni)

Activationsame as MWM-1(Co/2Ni); drying temperature not separately stated for each ratio

Scalability contextNo single crystals obtained for the additional Co/xNi ratios; PXRD showed similar structures and good crystallinity.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CoCl2.6H2O	variable molar ratio to NiCl2.6H2O	3 · Section 2.4.3
Metal Source	NiCl2.6H2O	variable molar ratio to CoCl2.6H2O	3 · Section 2.4.3
Linker	H2mba	same method as MWM-1(Co/2Ni)	3 · Section 2.4.3
Base	NaOH	same method as MWM-1(Co/2Ni)	3 · Section 2.4.3
Solvent	anhydrous ethanol/deionised water	same method as MWM-1(Co/2Ni)	3 · Section 2.4.3

Complete recipeSource: Main

Route 4: Other

3 · Section 2.4.4

Metal precursorsZn(NO3)2.6H2O (0.25 mmol)

Linker precursorsbptp (0.5 mmol, 0.19 g)

SolventsDMF (10 mL); deionised water (10 mL + 5 mL); anhydrous ethanol (20 mL)

AdditivesKOH (25 mmol)

AtmosphereN2 during 700 C heat treatment

Temperature700

Time2

Oxidant / reductantKOH activation/carbonisation conditions

Work-upwashed three times with 2 M hydrochloric acid, deionised water and anhydrous ethanol

Activationheated to 700 C for 2 h under N2; dried at 80 C

Scalability contextApplication counter-electrode material, not a conductive MOF.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	bptp	0.5 mmol, 0.19 g	3 · Section 2.4.4
Solvent	DMF	10 mL	3 · Section 2.4.4
Metal Source	Zn(NO3)2.6H2O	0.25 mmol	3 · Section 2.4.4
Base	KOH	25 mmol	3 · Section 2.4.4
Solvent	anhydrous ethanol	20 mL	3 · Section 2.4.4
Acid	hydrochloric acid	wash · 2 M	3 · Section 2.4.4
Solvent	deionised water	10 mL + 5 mL; wash	3 · Section 2.4.4