Synthesis · Controlling the Thermoelectric Properties of Organometallic Coordination Polymers via Ligand Design

3 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Other

9 · Synthetic procedures - Ni-btt

Metal precursorsnickel acetate tetrahydrate (NiAc2 . 4 H2O; 1.17 g, 4.70 mmol)

Linker precursors1,2,4,5-tetrakis(isopropylthio)benzene (4; 1.76 g, 4.70 mmol), prepared from 1,2,4,5-tetrachlorobenzene and 2-propanethiol in DMA with NaOH

Solventsanhydrous N,N-dimethylacetamide (75 mL); thoroughly degassed water (15 mL plus 20 mL nickel acetate solution); deionised water and methanol for Soxhlet purification

Additivessodium metal (5.40 g, 235 mmol)

Atmospherenitrogen atmosphere using standard Schlenk techniques; degassed water used in metal addition

Temperature100 degC for dealkylation and polymerisation; dried at 100 degC under vacuum

Time24 h with sodium at 100 degC; nickel acetate added over 15 min; 24 h at 100 degC after addition; Soxhlet 24 h water plus 24 h methanol; vacuum dry 24 h

Oxidant / reductantsodium dealkylation to benzene-1,2,4,5-tetrathiolate intermediate

Work-upCool to room temperature; collect black solid by centrifugation; Soxhlet extract with deionised water then methanol; dry under vacuum.

Activationdried for 24 h in vacuum at 100 degC

Scalability contextBulk powder synthesis reported at 1.76 g precursor 4 scale; purified black powder yield 0.60 g, 2.30 mmol, 49%.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1,2,4,5-tetrakis(isopropylthio)benzene (4)	1.76 g, 4.70 mmol	9 · Synthetic procedures - Ni-btt
Solvent	anhydrous N,N-dimethylacetamide	75 mL	9 · Synthetic procedures - Ni-btt
Reductant	sodium	5.40 g, 235 mmol	9 · Synthetic procedures - Ni-btt
Solvent	thoroughly degassed water	15 mL plus 20 mL for nickel acetate	9 · Synthetic procedures - Ni-btt
Metal Source	nickel acetate tetrahydrate (NiAc2 . 4 H2O)	1.17 g, 4.70 mmol	9 · Synthetic procedures - Ni-btt
Solvent	deionized water	Soxhlet 24 h	9 · Synthetic procedures - Ni-btt
Solvent	methanol	Soxhlet 24 h	9 · Synthetic procedures - Ni-btt

Complete recipeSource: Both

Route 2: Other

8 · Synthetic procedures - Ni-diett

Metal precursorsnickel acetate tetrahydrate (NiAc2 . 4 H2O; 0.65 g, 2.61 mmol)

Linker precursorscompound 2, [2,2'-bi[1,3]dithiolo[4,5-d][1,3]dithiolylidene]-5,5'-dione (1.00 g, 2.60 mmol), prepared by refluxing compound 1 with triethyl phosphite in toluene

Solventsanhydrous methanol for polymerisation; 20 mL anhydrous methanol for nickel acetate; deionised water and methanol for Soxhlet purification

Additivessodium methoxide (0.65 g; text reports 120 mmol)

Atmospherenitrogen atmosphere using standard Schlenk techniques; anhydrous methanol

Temperaturemethanol reflux; dried at 100 degC under vacuum

Time24 h linker/base reflux; nickel acetate added over 30 min; additional 24 h heating; Soxhlet water and methanol both 24 h; vacuum dry 24 h

Oxidant / reductantsodium methoxide forms tetraanion intermediate; compound 2 precursor formed by triethyl phosphite reductive dimerisation of compound 1

Work-upCool to room temperature; filter black precipitate; Soxhlet extract with deionised water then methanol; dry under vacuum.

Activationdried for 24 h in vacuum at 100 degC

Scalability contextBulk powder synthesis reported at 1.00 g compound 2 scale; purified black powder yield 0.75 g, 1.94 mmol, 75%.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	compound 2	1.00 g, 2.60 mmol	8 · Synthetic procedures - Ni-diett
Base	sodium methoxide	0.65 g, 120 mmol	8 · Synthetic procedures - Ni-diett
Solvent	anhydrous methanol	not stated for initial solution; 20 mL for nickel acetate solution	8 · Synthetic procedures - Ni-diett
Metal Source	nickel acetate tetrahydrate (NiAc2 . 4 H2O)	0.65 g, 2.61 mmol	8 · Synthetic procedures - Ni-diett
Solvent	deionized water	Soxhlet 24 h	8 · Synthetic procedures - Ni-diett
Solvent	methanol	Soxhlet 24 h	8 · Synthetic procedures - Ni-diett

Complete recipeSource: Both

Route 3: Other

8 · Synthetic procedures - Poly(nickel-ethylenetetrathiolate) (Ni-ett)

Metal precursorsnickel acetate tetrahydrate (NiAc2 . 4 H2O; 1.20 g, 4.82 mmol)

Linker precursors1,3,4,6-tetrathiapentalene / compound 1 (1.00 g, 4.81 mmol), prepared from methyl dichloroacetate and potassium isopropylxanthate via compound 6 and acid cyclisation

Solventsanhydrous methanol (50 mL for ligand/base reflux; 30 mL for nickel acetate solution); deionised water and methanol for Soxhlet purification

Additivessodium methoxide (1.20 g, 22.2 mmol)

Atmospherenitrogen atmosphere using standard Schlenk techniques; anhydrous methanol

Temperaturemethanol reflux; dried at 100 degC under vacuum

Time24 h ligand/base reflux plus 24 h after nickel addition; Soxhlet 24 h water plus 24 h methanol; vacuum dry 24 h

Oxidant / reductantsodium methoxide generates thiolate/tetraanion intermediate

Work-upCool to room temperature, filter crude black Ni-ett; Soxhlet extract with deionised water then methanol; dry under vacuum.

Activationdried for 24 h in vacuum at 100 degC

Scalability contextBulk powder synthesis reported at 1.00 g ligand scale; purified black powder yield 0.65 g, 3.08 mmol, 64%.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1,3,4,6-tetrathiapentalene 1	1.00 g, 4.81 mmol	8 · Synthetic procedures - Poly(nickel-ethylenetetrathiolate) (Ni-ett)
Base	sodium methoxide	1.20 g, 22.2 mmol · excess	8 · Synthetic procedures - Poly(nickel-ethylenetetrathiolate) (Ni-ett)
Solvent	anhydrous methanol	50 mL + 30 mL	8 · Synthetic procedures - Poly(nickel-ethylenetetrathiolate) (Ni-ett)
Metal Source	nickel acetate tetrahydrate (NiAc2 . 4 H2O)	1.20 g, 4.82 mmol	8 · Synthetic procedures - Poly(nickel-ethylenetetrathiolate) (Ni-ett)
Solvent	deionized water	Soxhlet 24 h	8 · Synthetic procedures - Poly(nickel-ethylenetetrathiolate) (Ni-ett)
Solvent	methanol	Soxhlet 24 h	8 · Synthetic procedures - Poly(nickel-ethylenetetrathiolate) (Ni-ett)