New Phases Through Pressure

New Phases Through Pressure


Gregory J. Halder and colleagues, Argonne National Laboratory, Argonne, IL, USA, have demonstrated that pressure offers a novel approach for generating new phases and exploring the structure-property relationships of molecular materials.

The team used in situ synchrotron powder diffraction to probe the pressure-dependent structural transformation of α-Co(dca)2 [dca = dicyanamide or N(CN)2] to the high-pressure phase γ-Co(dca)2. This orthorhombic (Pmnn) to monoclinic (P21/n) transformation occurs at 1.1 GPa. The mechanism is driven by a combination of destabilizing factors within α-Co(dca)2, including the elongation of the Co(II) octahedra and the strain on the amide bond angle of the ligand. The reduction in symmetry for γ-Co(dca)2 leads to a tilting effect in the crystal packing, asymmetry in the coordination binding geometries of the cyanide groups of the ligands, and a pronounced rotation of the Co(II) octahedral at high pressures.

Image: Cobalt(II) octahedral packing diagram as viewed in the (001) plane. © Yakovenko et al.


Leave a Reply

Kindly review our community guidelines before leaving a comment.

Your email address will not be published. Required fields are marked *