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Pressure-Driven Orbital Reorientations and Coordination-Sphere Reconstructions in [CuF2(H2O)2(pyz)]

DOI: 10.1002/ange.201202367 DOI Help

Authors: Alessandro Prescimone (The University of Edinburgh) , Chelsey Morien (Florida State University) , Dave Allan (Diamond Light Source) , John A. Schlueter (Argonne National Laboratory) , Stan Tozer (National High Magnetic Field Laboratory, Florida State University) , Jamie Manson (Eastern Washington University) , Simon Parsons (The University of Edinburgh) , Euan K. Brechin (The University of Edinburgh) , Stephen Hill (Florida State University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Angewandte Chemie , VOL 124 (30) , PAGES 7608 - 7612

State: Published (Approved)
Published: July 2012
Diamond Proposal Number(s): 6146

Abstract: The application of pressure in the study of molecule-basedmaterials has gained considerable recent interest, in part dueto the high compressibilities of these materials, but alsobecause the relevant electronic/magnetic (low-energy)degrees of freedom in such materials are often very sensitiveto pressure.[1–11]For example, small changes in the coordina-tion environment around a magnetic transition-metal ion canproduce quite dramatic variations in both the on-site spin–orbit coupling as well as the exchange interactions betweensuch ions when assembled into three-dimensional (3D)networks.[2–5]However, perhaps the most compelling reasonto use pressure as a tool for understanding magneto-structuralcorrelations is the possibility of focusing investigations ona single molecule or material, as opposed to using chemicalmeans to influence the coordination environment arounda metal center, for example, by studying families of seeminglyrelated complexes that vary only in the identity of thecoordinating ligands. The latter approach obviously suffersfrom the “non-innocence” of ligands, particularly in the solidstate.The desire to study increasingly complex materials underpressure has spurred the development of sophisticatedspectroscopic tools that can be integrated with high-pressureinstrumentation.[12–15]The study of magneto-structural corre-lations requires not only precise crystallographic data, butalso detailed spectroscopic information concerning theunpaired electron(s) that give(s) rise to the magnetic proper-ties. Herein, we separately employ X-ray crystallography andhigh-frequency EPR spectroscopy to obtain high-resolutionstructural and magnetic data from oriented single-crystalsamples subjected to pressures of up to 3.5 GPa.We focus on the magnetic coordination polymer [CuF2-(H2O)2(pyz)] (1, pyz = pyrazine), which previous powderdiffraction studies have shown to undergo successive pres-sure-induced structural transitions, both of which are believedto involve dramatic reorientations of the Jahn–Teller (JT)axes associated with the CuIIions.

Subject Areas: Chemistry


Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 02/03/2016 14:50

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