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  • Title: Structural basis for the phase switching of bisaminecopper(II) cations at the thermal limits of lattice stability.
    Author: Naumov P, Sakurai K, Asaka T, Belik AA, Adachi S, Takahashi J, Koshihara SY.
    Journal: Inorg Chem; 2006 Jun 26; 45(13):5027-33. PubMed ID: 16780324.
    Abstract:
    The structural grounds of the decrease of point and lattice symmetries coupled with switching of the exchange interaction in single crystals of a highly strained, coordinationally unsaturated bisdiaminecopper(II) cation are described. The combined magnetic susceptibility and X-ray diffraction results indicate that the interplay between the inherent vibronic instability and ligand-field strain imposed by moderately flexible, coordinationally shielding ligands enables effective switching of the pseudo-Jahn-Teller d9 centers between states with different exchange interaction in the low-temperature regime and valence orbital orientation and coordination geometry in the high-temperature regime. Within the low-temperature hysteresis region, the phase transition can also be induced by excitation of the ligand-to-metal charge-transfer bands, resulting in overall shrinkage of the lattice. The compound is a prototype of weakly electronically coupled one-dimensional Jahn-Teller systems, which can undergo phase transitions induced by light, in addition to heating, cooling, and change of pressure, and it represents a prospective basis for the design of switching materials capable of multimode external control.
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