Vapochromic behaviour of a nickel(ii)-quinonoid complex with dimensional changes between 1D and higher

Abstract

The nickel(II)–chloranilato complex {Ni(ca)(VM)₂}_n (H₂ca = chloranilic acid, VM = coordinated vapour molecules, such as water) shows reversible vapochromism upon exposure to various vapours and subsequent drying by heating. In contrast to the Ni(II)-quinonoid complex, [Ni(HL^Me)₂] (H₂L^Me = 4-methylamino-6-methyliminio-3-oxocyclohexa-1,4-dien-1-olate), which was reported to exhibit vapochromic spin-state switching between high and low spin states, the chloranilato complex does not change its spin state even after the removal of coordinated vapour molecules. X-ray absorption fine structure (XAFS) analysis revealed that the six-coordinate geometry of {Ni(ca)(VM)₂}_n was maintained even after the removal of vapour molecules, in contrast to the [Ni(HL^Me)₂] complex. The unique vapochromism that follows the dimensional change between 1D and higher is influenced by the relatively weaker ligand field of the chloranilate ligand.