• Photophysical properties of three-dimensional transition metal tris-oxalate network structures
    A. Hauser, M.E. Von Arx, V.S. Langford, S. Kairouani, U. Oetliker and A. Pillonnet
    in "Topics in Current Chemistry, Transition Metal and Rare Earth Compounds. Excited States, Transitions, and Interactions, Vol III" (ed. H. Yersin), Springer, Berlin, 241 (2004)
    DOI:10.1007/b96860 | unige:3941
Excitation energy transfer processes play an important role in many areas of physics, chemistry and biology. The three-dimensional oxalate networks of composition [MIII(bpy)3][MIMIII(ox)3]ClO4 (bpy=2,2-bipyridine, ox=oxalate, MI=alkali ion) allow for a variety of combinations of different transition metal ions. The combination with chromium(III) on both the tris-bipyridine as well as the tris-oxalate site constitutes a model system in which it is possible to differentiate unambiguously between energy transfer from [Cr(ox)3]3– to [Cr(bpy)3]3+ due to dipole-dipole interaction on the one hand and exchange interaction on the other hand. Furthermore it is possible to just as unambiguously differentiate between the common temperature dependent phonon-assisted energy migration within the 2E state of [Cr(ox)3]3–, and a unique resonant process.
In this paper we discuss on the quantum efficiency in spin crossover compounds. Spin crossover solids are text-book examples of photo switchable materials that present a thermal spin transition from the diamagnetic low-spin state, thermodynamically stable at low temperatures, to the paramagnetic high-spin state becoming the thermodynamically stable state at elevated temperature. By irradiating them with an appropriate wavelength, they can pass from the stable low spin state to the metastable high spin state at temperatures below the thermal transition temperature. For the compound [Fe(pic)3]Cl2·EtOH, the question regarding the quantum efficiency of the photo-conversion process that is the number of molecules converted by one single photon and its possible dependency on irradiation intensity gave rise to a controversy. The experimental results presented in this paper demonstrate that the quantum efficiency of the photo-conversion at 11 K is on the order of unity, with no noticeable dependency of the quantum efficiency on light intensity. It does, however, depend to a small extent on the fraction of complexes already converted to the high-spin state.
  • Resonant Energy Transfer in the Mixed Crystal Series [Rh(bpy)3][NaAlxCr1-x(ox)3]ClO4 (bpy = 2,2'-bipyridine, ox = Oxalate, x = 0.05-1)
    M.E. Von Arx, V.S. Langford, U. Oetliker and A. Hauser
    Journal of Physical Chemistry A, 106 (31) (2002), p7099-7105
    DOI:10.1021/jp0201736 | unige:3682 | Abstract | Article HTML | Article PDF
Efficient resonant energy transfer occurs within the R1 line of the 4A2 → 2E transition of the [Cr(ox)3]3- chromophore in mixed crystal [Rh(bpy)3][NaAl1-xCrx(ox)3]ClO4 (x = 0.05−0.9, ox = oxalate, bpy = 2,2‘-bipyridine). This manifests itself in the form of multiline patterns in resonant fluorescence line narrowing (FLN) experiments at 1.5 K. The conditions for such a resonant process to occur are that the inhomogeneous line width of the R1 line is larger than the zero-field splitting of the ground state, which, in turn, is larger than the homogeneous line width of the transition. The number of lines and their relative intensities depend critically upon the [Cr(ox)3]3- concentration and the excitation wavelength within the inhomogeneous distribution. The basic model for resonant energy transfer as presented by von Arx et al. (Phys. Rev B 199654, 15800) is extended to include the effects of diluting the chromophores in an inert host lattice and of nonresonant R2 excitation. In addition, Monte Carlo simulations serve to explain the temporal evolution of the multiline pattern following pulsed excitation.
 
[Fe(pic)3]Cl2·EtOH (pic = 2-picolylamine) is a spin-crossover compound that can be converted from the low-spin state to the high-spin state at temperatures below the thermal transition temperature by way of light irradiation in the visible part of the electromagnetic spectrum. For this compound, the question regarding the quantum efficiency of this photoconversion process and its possible dependence on irradiation intensity gave rise to some controversy. The experimental results presented in this paper demonstrate that the quantum efficiency of the photoconversion at 11 K is on the order of unity, with no noticeable dependence on irradiation intensity. It does, however, depend to some extent on the fraction of complexes already converted to the high-spin state.

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