cMOF Evidence Base

Synthesis evidence

Polyethenetetrathiolate or polytetrathiooxalate? Improved synthesis, a comparative analysis of a prominent thermoelectric polymer and implications to the charge transport mechanism

Tkachov R., Stepien L., Grafe R. et al. · Polymer Chemistry · 2018 · 4543-4555

6 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Other

10 · Experimental - Synthesis of polymers

Metal precursorsnickel(II) chloride hexahydrate, 1.141 g (4.8 mmol)
Linker precursors1,3,4,6-tetrathiapentalene-2,5-dione (TPD), 1.0 g (4.8 mmol), converted with potassium methoxide
Solventsmethanol; 20 ml for KOMe/TPD and 80 ml MeOH for NiCl2 solution
Additivespotassium methoxide, 1.557 g (22.2 mmol; 4.6 equivalents)
AtmosphereInitially inert atmosphere/glovebox unless otherwise indicated; vessel opened in air for 30 min oxidation before aqueous workup.
Temperature80 C reflux then room temperature air exposure
Time20 h TPD/KOMe reflux + 20 h after NiCl2 addition + 0.5 h air exposure
Oxidant / reductantAir oxygen during final vessel opening and workup acts as oxidant.
Work-up100 ml water added and shaken; black precipitate suction-filtered, washed with water and MeOH.
ActivationDried under vacuum at room temperature overnight.
Scalability contextAuthors state TPD-derived methods are sensitive to details of oxidation/air exposure.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Basepotassium methoxide1.557 g (22.2 mmol; 4.6 equivalents)10 · Experimental - Synthesis of polymers
Linker1,3,4,6-tetrathiapentalene-2,5-dione1.0 g (4.8 mmol)10 · Experimental - Synthesis of polymers
Metal Sourcenickel(II) chloride hexahydrate1.141 g (4.8 mmol)10 · Experimental - Synthesis of polymers
Solventmethanol20 ml + 80 ml10 · Experimental - Synthesis of polymers
Oxidantair/oxygen30 min exposure10 · Experimental - Synthesis of polymers
Complete recipeSource: Main

Route 2: Other

10 · Experimental - Synthesis of polymers

Metal precursorsnickel(II) chloride hexahydrate, 1.141 g (4.8 mmol)
Linker precursorsTPD, 1.0 g (4.8 mmol), converted with potassium methoxide
Solventsmethanol for initial TPD/KOMe; N-methylformamide (NMF) for NiCl2 solution; main discussion describes MeOH:NMF mixture 1:4
Additivespotassium methoxide, 1.557 g (22.2 mmol; 4.6 equivalents)
AtmosphereInitially inert atmosphere/glovebox unless otherwise indicated; vessel opened in air for 30 min before water workup.
Temperature80 C reflux then room temperature air exposure
Time20 h TPD/KOMe reflux + 20 h after NiCl2 addition + 0.5 h air exposure
Oxidant / reductantAir oxygen during final vessel opening and workup.
Work-up100 ml water added and shaken; black precipitate suction-filtered, washed with water and MeOH.
ActivationDried under vacuum at room temperature overnight.
Scalability contextOptimisation did not substantially reduce K content; method remains oxidation-sensitive.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Basepotassium methoxide1.557 g (22.2 mmol; 4.6 equivalents)10 · Experimental - Synthesis of polymers
Linker1,3,4,6-tetrathiapentalene-2,5-dione1.0 g (4.8 mmol)10 · Experimental - Synthesis of polymers
Metal Sourcenickel(II) chloride hexahydrate1.141 g (4.8 mmol)10 · Experimental - Synthesis of polymers
Solventmethanol and N-methylformamide20 ml MeOH + 80 ml NMF10 · Experimental - Synthesis of polymers
Oxidantair/oxygen30 min exposure10 · Experimental - Synthesis of polymers
Complete recipeSource: Main

Route 3: Other

10 · Experimental - Synthesis of polymers

Metal precursorsnickel(II) chloride hexahydrate, 1.141 g (4.8 mmol)
Linker precursorsTPD, 1.0 g (4.8 mmol), with potassium methoxide
Solventsmethanol; 20 ml for KOMe/TPD and 25 ml MeOH for NiCl2 solution
Additivespotassium methoxide, 1.557 g (22.2 mmol; 4.6 equivalents)
AtmosphereOxygen-free; black precipitate filtered in glovebox and washed with deionized degassed water and dry methanol.
Temperature18 C
Time96 h
Oxidant / reductantNo intentional oxidant; designed to avoid oxidation.
Work-upFiltered in glovebox; washed with deionized degassed water and dry methanol.
ActivationDried under vacuum at room temperature overnight.
Scalability contextPrepared as a negative reference with strongly charged backbone.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Basepotassium methoxide1.557 g (22.2 mmol; 4.6 equivalents)10 · Experimental - Synthesis of polymers
Linker1,3,4,6-tetrathiapentalene-2,5-dione1.0 g (4.8 mmol)10 · Experimental - Synthesis of polymers
Metal Sourcenickel(II) chloride hexahydrate1.141 g (4.8 mmol)10 · Experimental - Synthesis of polymers
Solventmethanol20 ml + 25 ml10 · Experimental - Synthesis of polymers
Partial recipeSource: Both

Route 4: Other

27 · Scheme of tentative polymerization mechanism · Scheme SE1

Metal precursorsP2 polymer from route_p2
Linker precursorsP2 polymer from route_p2
Solventswater under open atmosphere; dry methanol wash before drying
AtmosphereOpen atmosphere during water washing; air oxygen implicated in post-polymerisation oxidation.
Temperatureroom temperature
Oxidant / reductantAir oxygen during washing in open atmosphere.
Work-upWashing P2 with water under open atmosphere; dried under vacuum at room temperature overnight.
ActivationDried under vacuum at room temperature overnight.
Scalability contextMechanistic SI scheme attributes formation of P2-ox to post-polymerisation oxidation during washing.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Oxidantair oxygenopen atmosphere during washing27 · Scheme of tentative polymerization mechanism · Scheme SE1
Solventwaterwash27 · Scheme of tentative polymerization mechanism · Scheme SE1
Complete recipeSource: Main

Route 5: Other

10 · Experimental - Synthesis of polymers

Metal precursorsnickel(II) chloride hexahydrate, 1.141 g (4.8 mmol)
Linker precursorspotassium tetrathiooxalate K2tto, 1.557 g (22.2 mmol; text says 4.6 equivalents)
SolventsN-methylformamide; 20 ml for K2tto and 25 ml for NiCl2 solution
Additivesnone reported
AtmosphereK2tto solution added to NiCl2 solution, then water added under ambient atmosphere.
Temperatureroom temperature
Time0.167 h stirring before water addition
Oxidant / reductantNo added oxidant/reductant; K2tto is the oxidized true monomer.
Work-up100 ml water added under ambient atmosphere and shaken; black precipitates suction-filtered, washed with water and MeOH.
ActivationDried under vacuum at room temperature overnight.
Scalability contextAuthors describe the reaction as simple, fast, room-temperature and almost insensitive to time, temperature and air exposure.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Linkerpotassium tetrathiooxalate1.557 g (22.2 mmol; 4.6 equivalents)10 · Experimental - Synthesis of polymers
Metal Sourcenickel(II) chloride hexahydrate1.141 g (4.8 mmol)10 · Experimental - Synthesis of polymers
SolventN-methylformamide20 ml + 25 ml10 · Experimental - Synthesis of polymers
Solventwater100 ml10 · Experimental - Synthesis of polymers
Vague recipeSource: Main

Route 6: Other

10 · Experimental - Synthesis of polymers

Metal precursorspoly[Ni-tto] P3
Linker precursorspoly[Ni-tto] P3
Solventsvapour treatment in desiccator
Additiveshydrazine vapours or HCl vapours
AtmosphereDesiccator; Fig. 7 caption states samples obtained by exposure under oxygen-free conditions.
Temperatureroom temperature assumed; not specified
Timenot specified
Oxidant / reductantHydrazine reductant or HCl acid vapour treatment.
Work-upnot specified
Activationnot specified
Scalability contextReactant vapour concentration and time of exposure did not strongly alter observed results within device error.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Reductanthydrazine vapoursnot specified10 · Experimental - Synthesis of polymers
AcidHCl vapoursnot specified10 · Experimental - Synthesis of polymers