Structural phase transition in a charge-transfer compound: tropylium...

Molecular motion in crystals has attracted much attention for the development of stimuli-responsive materials. The most studied are molecules with few atoms or highly symmetrical molecules. To develop molecules with new motion characteristics, we synthesized a charge-transfer compound, namely, tropylium hexafluoridoantimonate(V)-1,4-dimethylnaphthalene (1/1), (C₇H₇)[SbF₆]·C₁₂H₁₂, and studied its structural phase transition. In this compound, the tropylium cation and the 1,4-dimethylnaphthalene molecule have planar geometry, but the latter has low symmetry. They are stacked as a one-dimensional chain structure through π-π charge-transfer interactions. Weak intermolecular interactions and planar molecular geometry result in a large degree of freedom of in-plane motion. Upon heating, due to the in-plane rotation of the molecules, the compound undergoes an order-disorder structural phase transition (phase-transition temperature = 334 K). The space group of the room-temperature phase is P2₁/m and the space group of the high-temperature phase is P4/mmm. This phase transition is accompanied by significant dielectric anomalies. The current investigation shows that the structural features of the title compound can be used to construct functional materials with phase transitions, such as molecular ferroelectrics.