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Structural basis for the phase switching of bisaminecopper(II) cations at the thermal limits of lattice stability.
- Source :
-
Inorganic chemistry [Inorg Chem] 2006 Jun 26; Vol. 45 (13), pp. 5027-33. - Publication Year :
- 2006
-
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.
Details
- Language :
- English
- ISSN :
- 0020-1669
- Volume :
- 45
- Issue :
- 13
- Database :
- MEDLINE
- Journal :
- Inorganic chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 16780324
- Full Text :
- https://doi.org/10.1021/ic060110s