Solvent-drop assisted mechanochemical synthesis of the black and green polymorphs of the tetrathiafulvalene–chloranil charge transfer salt

This work describes the synthesis of the green and black polymorphic forms of the tetrathiafulvalene–chloranil (TTF–CA) charge transfer salt as pure phases, by solvent-assisted mechanochemistry. Both materials were characterized using laboratory and high-resolution X-ray powder diffraction (XRPD), elemental analysis and scanning electron microscopy (SEM). The high-resolution XRPD pattern of the TTF–CA black polymorph was indexed with a triclinic lattice a = 10.756(5) Å, b = 11.057(4) Å, c = 6.614(2) Å, α = 101.36(2)°, β = 93.69(3)°, γ = 89.37(3)°, V = 769.6(5) Å3. The chemical stability of these phases upon heating was investigated using thermogravimetric analysis (TGA), elemental analysis and X-ray powder diffraction (XRPD), indicating that both polymorphs undergo chemical decomposition, and ruling out the transition to an air-stable high temperature polymorph.

► The green and black polymorphs of TTF–CA were synthesized by mechanochemistry.
► We report the lattice parameters of the TTF–CA black polymorph.
► Both TTF–CA polymorphs undergo chemical decomposition upon heating under air.