An ionic-liquid-containing 2D coordination polymer was synthesized via a solvent-free reaction. The material exhibited incongruent melting at 112 °C, forming a solid–liquid mixture; further heating to 240 °C led to...
Several meltable coordination polymers (CPs) that possess
substantial
advantages attributable to their high flexibility and processability
have been developed recently; however, the melting mechanism and vitrification
conditions of these materials are not yet fully understood. In this
study, we synthesized meltable CPs [A][K(TCM)2] (A = onium
cation, TCM = C(CN)3
–) incorporating
ionic liquid components and investigated their crystal structures
and melting behaviors in detail. These CPs feature two- or three-dimensional
anionic [K(TCM)2]
n
– frameworks incorporating onium cations. Each CP was found to undergo
incongruent melting at a temperature between 73 and 192 °C to
produce a heterogeneous mixture of the ionic liquid ([A][TCM]) and
microcrystalline K[TCM]. Furthermore, they formed homogeneous liquids
upon further heating to ∼240 °C. The melting points of
these CPs were linearly correlated with those of their constituent
ionic liquids. The vitrification of these materials upon rapid cooling
from the molten state was further investigated. The cooling rates
required for vitrification differed greatly between the CPs and were
correlated with the cation flexibility.
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