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Vibronic behaviour of octahedral Cu(II) complexes in Cu(2-benzoylpyridine)2(NO3)2x2H2O crystal with a weak superexchange coupling. Temperature EPR studies

100%

Hoffmann S. K. , Goslar J. , Hilczer W. , Goher M. A. S.

Bulletin of the Polish Academy of Sciences. Chemistry

2000

tom Vol. 48, No. 4

397-409

Octahedral [Cu(2-benzoylpyridine)2 (H20)2] complexes in the Cu(2-Bzpy)2-(NO3)2 .2H2O are very dynamical and Cu(II) ions are very weakly coupled as it is shown by the single crystal EPR measurements in the temperature range 4.2-300 K. Rigid lattice limit (9 K) of spin-Hamiltonian parameters are: gx = 2.137, gy = 2.014, gz = 2.306 as determined by decoupling of exchange merged EPR lines. The ground state is predominantly Ix(2) -y(2)) with 8% of the Iz(2)) state. This mixing is produced by zero-point motions in the ground vibrational state and results in g x > gy with strong lowering of the gy-value. The decoupling procedure gave superexchange coupling parameter J = 0.0040 cm(1), which unexpectedly is temperature independent in contrast to other weakly coupled Cu(II) paramagnets. The g-factors show relatively strong temperature variations with gy practically not affected by temperature and a tendency to averaging of the g x and gz with room tem-perature parameters: g x = 2.161, gy = 2.013, gz = 2.285. This is explained as the pseudo Jahn-1eller effect with dynamical transitions between two elongated octahedral axes, i.e. O-Cu-O (x-axis) and H2O-Cu-H2O (z-axis) with N-Cu-N (y-axis) direction ill the in-plane coordination with pyridine nitrogen not affected by vibronic dynamics. The vibronic effect can be described by two-well model in the temperature range 80-150 K only with energy difference between the ground vibronic state in the well being 220 cm-l. At lower temperatures Cu(II) complexes are strongly localized in the deepest potential well, whereas at higher temperatures, the vibronic g-factor averaging is dominated by the other mechanism.

Manufacture of calcium formate from sodium formate

70%

Trybuła S. W. , Terelak K. L.

tom Vol. 5, nr 3

17-18

The concept of calcium formate process with the use of a double exchange reaction between sodium formate and calcium nitrate has been proposed. In order to choose the optimum technological version of that process, the preliminary research work was performed.