Spectral sensitive phonon wipeout due to a fluctuating spin state in a Fe2+ coordination polymer

Raman scattering in the spin-crossover system [Fe(pmd)(H2O){Au(CN)2}2]*H2O reveals a complex three-phase spin-state transition in contrast to earlier observations in magnetization measurements. We observe different spin state phases as function of temperature and electromagnetic radiation in the visible spectral range. There exists a fluctuating spin state phase with an unexpected wipeout of the low frequency phonon scattering intensity. Furthermore we observe one phase with reduced symmetry that is attributed to a cooperative Jahn-Teller effect. Pronounced electron-phonon interaction manifests itself as a strong Fano-resonance of phonons related to {FeN6} and {FeN4O2} coordination octahedra. Density functional theory supports this interpretation.Comment: 9 pages, 9 figures, 3 table

Crystallographic elucidation of purely structural, thermal and light-induced spin transitions in an iron(ii) binuclear complex

The intricate phase diagram of the binuclear iron(ii) spin-crossover complex [{Fe(3-bpp)(NCS)2}2(4,4�-bypiridine)] ·2CH3OH where 3-bpp is 2,6-bis(pyrazol-3-yl)pyridine has been investigated by variable temperature single crystal X-ray diffraction including a study into the effect of photo-irradiation. This sample is known to exhibit an incomplete spin transition at low temperature. At room temperature, in phase I, iron ions are all crystallographically equivalent, adopting the high spin state (HS). X-Ray structural investigation has revealed two phase transitions in the range (300-30 K). The first transition (T�161 K) leading to phase II is of a purely structural nature and corresponds to a break in symmetry as a result of a twist of the two rings of 4,4�-bipyridine; the two iron sites of the binuclear unit becoming crystallographically independent but remaining all HS. The second structural transition corresponds to the spin crossover, one of the two Fe(ii) ions of the binuclear complex being in the low spin state (LS) in phase III. The crystal structure shows an ordered HS-LS crystal packing where HS and LS sites are clearly identified and not randomly distributed in the metal ion sites as often observed. Moreover, light irradiation of single crystals in phase III at 30 K, leading to phase III*, induces a light-induced spin-state trapping (LIESST) effect corresponding to the full conversion of all the iron sites to HS. The crystal packing in phase III* is closer to that of phase III than to those observed in the other HS phases, I and II. This reveals an unusual differentiation between the thermal and light-induced HS states. A deeper analysis of the structural properties first demonstrates the key role of the bipyridine bridge in the peculiar preliminary pure structural transition shown by the title compound. Elsewhere, it also shows that the molecular packing is strongly dependent on the nature of the external perturbation contrary to the iron coordination sphere geometry that appears to be only dependent on the spin state. Moreover, in the HS phase II, the distortion of the iron sites that will subsequently undergo a spin crossover demonstrates some differences with the distortion of the iron sites that remain HS. The predominant role of the iron environment distortion in the spin crossover phenomenon is thus clearly evidenced. © 2010 The Royal Society of Chemistry