Back-Bonding Signature with High Pressure: Raman Studies on Silver Nitroprusside.

Abstract

In centrosymmetric molecules, like An+[M(CN)6]n- (where A is alkali metal cation), normally all stretching vibrations of cyanide (CN-) shift to high frequency in response to nonhydrostatic pressure, whereas, in non-centrosymmetric molecules in which one axial CN ligand is replaced by NO ligand, one observes unusual softening of only equatorial CN stretching modes. This effect is pronounced when A+ is replaced by Ag+ with difference in coordination ability of latter, resulting in expression of characteristic signature of back-bonding. One can correlate this uneven stretching of cyanide to Poisson-like effect, where the axial Fe-N, Fe-C, and C-N stretching modes harden but the equatorial C-N stretching modes soften due to expansion at the equatorial plane. Thus, the present study is focused on results of non-hydrostatic high-pressure Raman measurements on silver nitroprusside up to 11.5 GPa, for not only observing characteristic signature of "back-bonding" interaction, rarely featured in literature, but also for generating reversible flexible structures akin to noncovalent interaction.