Synthesis · Redox Ladder of Ni3 Complexes with Closed-Shell, Mono-, and Diradical Triphenylene Units: Molecular Models for Conductive 2D MOFs

4 structured synthesis routes

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

Partial recipeSource: SI

Route 1: Electrochemical

SI p004 and p009 / printed pp.3,8 · Synthesis of 1; Figure S4 caption · Scheme S1b; Figure S4

Metal precursorscrude [(Me3TPANi)3(HOTP)](BF4)n mixture containing Ni3HOTP cations

Linker precursorsHOTP-containing crude mixture

Solventsdichloromethane; tetrahydrofuran wash; dichloromethane and hexane for recrystallisation

AdditivesTBAPF6 supporting electrolyte

Atmospherenitrogen-filled glovebox

Temperatureroom temperature, not explicitly specified

Timeuntil current dropped below 1% of initial value for 0.5 h

Substrate orientationH-cell with Pt mesh working and counter electrodes; Ag/AgCl wire reference electrode

Oxidant / reductantconstant-potential electrolysis at -0.2 V with respect to the open-circuit potential

Work-upWorking-electrode solution dried under vacuum; washed thoroughly with tetrahydrofuran to remove TBAPF6; recrystallised twice by layering hexane onto dichloromethane solution.

Scalability contextYield reported as 72%; no scale-up discussion.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	crude mixture [(Me3TPANi)3(HOTP)](BF4)n	not specified	SI p004 and p009 / printed pp.3,8 · Synthesis of 1; Figure S4 caption · Scheme S1b; Figure S4
Electrolyte	TBAPF6	1.0 M in synthesis section; 0.2 M in electrolysis methods	SI p004 and p009 / printed pp.3,8 · Synthesis of 1; Figure S4 caption · Scheme S1b; Figure S4
Solvent	dichloromethane	Not specified	SI p004 and p009 / printed pp.3,8 · Synthesis of 1; Figure S4 caption · Scheme S1b; Figure S4
Solvent	tetrahydrofuran	wash solvent	SI p004 and p009 / printed pp.3,8 · Synthesis of 1; Figure S4 caption · Scheme S1b; Figure S4
Solvent	hexane	layering solvent	SI p004 and p009 / printed pp.3,8 · Synthesis of 1; Figure S4 caption · Scheme S1b; Figure S4

Complete recipeSource: Both

Route 2: Other

SI p005 / printed p.4 · Synthesis of 2 · Scheme S1c

Metal precursors150 mg complex 1 in 30 mL dichloromethane

Linker precursorsHOTP-containing complex 1

Solventsdichloromethane; tetrahydrofuran; hexane

Atmospherenitrogen glovebox

Temperatureroom temperature, not explicitly specified

Time0.5

Oxidant / reductant24.6 mg ferrocenium tetrafluoroborate in 10 mL dichloromethane, one-electron oxidation

Work-upRemoved all solvent under vacuum; dissolved solid in minimal dichloromethane; precipitated by adding tetrahydrofuran to remove ferrocene and unreacted oxidant; centrifuged; washed twice with hexane; recrystallised twice by hexane layering onto dichloromethane solution.

Scalability contextYield reported as 92%; no scale-up discussion.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	complex 1	150 mg · in 30 mL dichloromethane	SI p005 / printed p.4 · Synthesis of 2 · Scheme S1c
Oxidant	ferrocenium tetrafluoroborate	24.6 mg · in 10 mL dichloromethane	SI p005 / printed p.4 · Synthesis of 2 · Scheme S1c
Solvent	dichloromethane	40 mL plus recrystallisation solvent	SI p005 / printed p.4 · Synthesis of 2 · Scheme S1c
Solvent	tetrahydrofuran	precipitation solvent	SI p005 / printed p.4 · Synthesis of 2 · Scheme S1c
Solvent	hexane	wash and layering solvent	SI p005 / printed p.4 · Synthesis of 2 · Scheme S1c

Complete recipeSource: Both

Route 3: Other

SI p005 / printed p.4 · Synthesis of 3 · Scheme S1d

Metal precursors150 mg complex 1 in 30 mL dichloromethane

Linker precursorsHOTP-containing complex 1

Solventsdichloromethane; hexane

Atmospherenitrogen glovebox

Temperatureroom temperature, not explicitly specified

Time0.5

Oxidant / reductant17.5 mg silver tetrafluoroborate, two-electron oxidation

Work-upRemoved all solvent under vacuum; washed resulting solid twice with hexane; recrystallised twice by layering hexane onto dichloromethane product solution.

Scalability contextYield reported as 78%; no scale-up discussion.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	complex 1	150 mg · in 30 mL dichloromethane	SI p005 / printed p.4 · Synthesis of 3 · Scheme S1d
Oxidant	silver tetrafluoroborate	17.5 mg	SI p005 / printed p.4 · Synthesis of 3 · Scheme S1d
Solvent	dichloromethane	30 mL plus recrystallisation solvent	SI p005 / printed p.4 · Synthesis of 3 · Scheme S1d
Solvent	hexane	wash and layering solvent	SI p005 / printed p.4 · Synthesis of 3 · Scheme S1d

Partial recipeSource: SI

Route 4: Other

SI p004 / printed p.3 · Synthesis of the crude mixture · Scheme S1a

Metal precursors34.6 mg Ni(BF4)2.6H2O in 3 mL methanol

Linker precursorsHHTP in 8 mL methanol; 33.8 mg Me3TPA in 3 mL methanol

Solventsmethanol; diethyl ether; dichloromethane and hexane for recrystallisation

Additives32 microL triethylamine in 3 mL methanol

Atmosphereair during synthesis; product transferred into a nitrogen glovebox after drying

Temperatureroom temperature reaction; -5 C overnight storage

Time0.75 h stirring plus overnight at -5 C

Work-upAdded 60 mL diethyl ether, stored at -5 C overnight, collected black-navy solid by filtration, washed twice with diethyl ether, dried thoroughly, transferred to nitrogen glovebox, recrystallised by layering hexane onto dichloromethane solution.

ActivationSolvents for glovebox work were dried and stored over activated 4 A molecular sieves; no framework activation reported.

Scalability contextProduct yield reported as 89%; no scale-up discussion.

Show 8 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(BF4)2.6H2O	34.6 mg · in 3 mL methanol	SI p004 / printed p.3 · Synthesis of the crude mixture · Scheme S1a
Linker	Me3TPA	33.8 mg · in 3 mL methanol	SI p004 / printed p.3 · Synthesis of the crude mixture · Scheme S1a
Linker	HHTP	not specified in extracted SI text · in 8 mL methanol	SI p004 / printed p.3 · Synthesis of the crude mixture · Scheme S1a
Base	triethylamine	32 microL · in 3 mL methanol	SI p004 / printed p.3 · Synthesis of the crude mixture · Scheme S1a
Solvent	methanol	17 mL total reported solution volume	SI p004 / printed p.3 · Synthesis of the crude mixture · Scheme S1a
Solvent	diethyl ether	60 mL plus wash solvent	SI p004 / printed p.3 · Synthesis of the crude mixture · Scheme S1a
Solvent	dichloromethane	used for recrystallisation solution	SI p004 / printed p.3 · Synthesis of the crude mixture · Scheme S1a
Solvent	hexane	layered onto dichloromethane solution	SI p004 / printed p.3 · Synthesis of the crude mixture · Scheme S1a