Synthesis · Aliovalent Substitution Tunes Physical Properties in a Conductive Bis(dithiolene) Two-Dimensional Metal-Organic Framework

Vague recipeSource: Main

Route 1: Other

2 · Results and Discussion - Synthesis · Figure 2A

Metal precursorsLi3Fe3(THT)2 shown in scheme; detailed precursor recipe not reproduced

Linker precursorsTHT linker in Li3Fe3(THT)2 precursor

Solventsnot reported in this paper

Additivesnot reported in this paper

Atmospheregeneral paper statement: N2-filled glovebox or N2 protection

Oxidant / reductant3 FcPF6 oxidation shown schematically from Li3Fe3(THT)2 to Fe3(THT)2

Work-upnot reported in this paper

Activationnot reported in this paper

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Li3Fe3(THT)2	not reported	2 · Results and Discussion - Synthesis · Figure 2A
Oxidant	FcPF6	3 equiv shown in scheme	2 · Results and Discussion - Synthesis · Figure 2A

Complete recipeSource: Both

Route 2: Other

7 · Experimental Section - Synthesis of Ni3(THT)2

Metal precursorsFreshly made Fe3(THT)2, 120 mg; NiCl2.6H2O, 0.2 M in DMF, 3 x 15 mL

Linker precursorsTHT linker already incorporated in Fe3(THT)2 precursor

SolventsDMF for NiCl2.6H2O soaks and washing; CH3CN washing solvent

Additivesnone reported

Atmosphereall syntheses and characterizations in N2-filled glovebox or under N2 protection; washing/drying handled air-free unless otherwise specified

Temperature70

Time144

Oxidant / reductantaliovalent transmetalation: Fe(III) substituted by Ni(II), inducing in situ oxidation of THT linker; no separate oxidant added in Ni step

Work-updecanted mother liquor and added fresh Ni solution every other day; after three soaks washed thoroughly with fresh DMF (3 x 15 mL) and CH3CN (3 x 15 mL) by soaking for a few hours followed by decanting

Activationdried under vacuum overnight at room temperature; porosity sample separately degassed at 80 deg C for 3 days to <1 mTorr/min

Scalability context120 mg Fe3(THT)2 gave 100 mg Ni3(THT)2 black powder, 83% yield.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Freshly made Fe3(THT)2	120 mg	7 · Experimental Section - Synthesis of Ni3(THT)2
Metal Source	NiCl2.6H2O	3 x 15 mL solution · 0.2 M in DMF	7 · Experimental Section - Synthesis of Ni3(THT)2
Solvent	DMF	3 x 15 mL wash plus soaking solvent	7 · Experimental Section - Synthesis of Ni3(THT)2
Solvent	CH3CN	3 x 15 mL wash	7 · Experimental Section - Synthesis of Ni3(THT)2

Aliovalent Substitution Tunes Physical Properties in a Conductive Bis(dithiolene) Two-Dimensional Metal-Organic Framework

2 structured synthesis routes