Vibrational properties and cooperativity of the 3D spin crossover network [Fe(pyrazine)][Pt(CN)₄]

Abstract

Nuclear inelastic scattering experiments and DFT calculations have been performed to explore the vibrational properties and molecular modes for the high-spin and low-spin phases of the spin crossover network [Fe(pyrazine)][Pt(CN)4].

Probing the SO2Adsorption Mechanism in Hofmann Clathrates via Inelastic Neutron Scattering and Density Functional Theory Calculations

“…In this region, the most intense bands predicted by the calculations for the bare material appear at 107.9 cm −1 and at 139 cm −1 , as shown in Figure 3. The first one corresponds to the rotation of the pyrazine around the z axis, in agreement with calculations by Hochdorffer et al 45 on a 3D molecular cluster composed of several repetitions of the clathrate unit cell. The second band includes three vibrational modes at energies of 137.8, 138.5, and 139.2 cm −1 .…”

“…The second peak at 138.5 cm −1 involves a rigid out-of-plane twisting of the Fe(CN 4 )N 2 octahedra, yielding a rigid twisting of the pyrazine about the y axis. This vibrational mode correponds to the one computed at 140 cm −1 in ref 45. The vibration at 139.2 cm −1 involves a large out-of-plane vibration of the cyanide together with a small libration of the pyrazine.…”

Probing the SO$_2$ adsorption mechanism in Hofmann clathrates via inelastic neutron scattering and density functional theory calculations

“…3. The first one corresponds to the rotation of the pyrazine around the z axis, in agreement with calculations by Hochdörffer et al 37 on a 3D molecular cluster composed of several repetitions of the clathrate unit cell. The second band includes 3 vibrational modes at energies 137.8, 138.5, and 139.2 cm −1 .…”

“…This vibrational mode correponds to the one computed at 140 cm −1 in ref. 37. The vibration at 139.2 cm −1 involves a large out-of-plane vibration of the cyanide together with a small libration of the pyrazine.…”

Vibrational properties of 1D- and 3D polynuclear spin crossover Fe(II) urea-triazoles polymer chains and quantification of intrachain cooperativity

“…Recently, we have demonstrated how the combination of NIS and DFT methods gives insight into vibrational and short range cooperative properties of 1D and 3D networks of Fe(II) SCO complexes [3,9,10]. The investigated 1D systems were based on the 1,2,4-triazole systems, displaying either an H or an amino group on 4 N. The synthesis and the SCO properties of the N-alkyl-substituted urea-and diurea-triazoles have been reported in an earlier work [11].…”