Journal
DALTON TRANSACTIONS
Volume 50, Issue 25, Pages 8696-8703Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1dt00269d
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Funding
- JSPS KAKENHI [JP17H06367, JP17H06372, JP18K19086, JP18K14232]
- Iketani Science and Technology Foundation
- Photon Factory Programme Advisory Committee [2019G511, 2018S2-002]
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The nickel(ii)-chloranilato complex displays reversible vapochromism even after the removal of coordinated vapour molecules, maintaining its spin state and six-coordinate geometry. The unique vapochromism, influenced by the weaker ligand field of the chloranilate ligand, is related to dimensional changes between 1D and higher dimensions.
The nickel(ii)-chloranilato complex {Ni(ca)(VM)(2)}(n) (H(2)ca = 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(HLMe)(2)] (H2LMe = 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(HLMe)(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.
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