Zakład Fizyki Wysokich Ciśnień - publikacje

Abstract: Four crystalline phases of the coordination compound [Ru(NH 3) 6](BF 4) 3 are identified by adiabatic calorimetry. Three phase transitions, one at T C3(IV→ III)=30.7 K, the second at T C2(III→II)=91.7 K (both accompanied by comparable entropy changes 3.0 and 3.1 J K -1 mol -1, respectively) and the third at T C1(II→I)=241.6 K (accompanied by an entropy change of 8.1 J K -1 mol -1) were discovered. X-ray single crystal diffraction (at 293 K) demonstrates that phase I is a highly dynamic disordered cubic phase (Fm3̄m, No. 225) with two types of BF4- anions differing in a degree of disorder. In phase II (at 170 K) the structure remains cubic (Ia3̄, No. 206), with two different types of cations and four different types of anions. Splitting of certain IR bands connected with NH 3 ligands at the observed phase transitions suggests a lowering of the symmetry of the [Ru(NH 3) 6] 3 complex cation. Both NH 3 ligands and BF4- anions perform fast reorientations (τ R≈10 -12 s), which are significantly slowed down below the phase transition at T C3. 1H NMR studies led to estimate the values of the activation energy of NH 3 ligands reorientation in the phases II and I as equal to ∼8 kJ mol -1. In phase I the whole hexammineruthenium(III) cations reorientation as a tumbling process can be noticed. The activation energy value of this motion is ∼24 kJ mol -1. 19F NMR studies give the values of the activation energy of BF4- anions reorientation as ∼6 kJ mol -1. Above the phase transition temperature half of BF4- anions perform a tumbling motion with E a≈8 kJ mol -1. © 2012 Elsevier Inc. All rights reserved.