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EPR and ESEEM Identification of Free Radicals and Molecular Structure of the Oligomers Formed During Polycondensation of 1-Chloro-4-nitrobenzene with Sodium Sulfides in N-Methyl-2-pyrrolidone

Hoffmann S., Polus I., Hilczer W., Goslar J., Kiczka S., Doczekalska B.

Polish Journal of Chemistry

2003

Vol. 77 / nr 1

87-98

The synthesis of derivative of poly (4-hydrazo-diphenylenedisulfide) by reaction of 1-chloro-4-nitrobenzene with sodium sulfide and disulfide in N-methyl-2-pyrrolidone leads to oligomeric products with average molecular weight of the homogeneous chains 1182 g/mol and 690 g/mol, respectively. The mechanisms of the reactive intermediates polycondensation reaction are described. The products were characterized by IR, 1H NMR, and EPR spectroscopy and by elemental analysis. The final amorphous oligomer products contain mostly diamagnetic species and about 1% of paramagnetic species. The latter produce strong isotropic EPR signal at g = 2.0025 from free radical with concentration of about 1018 radicals/gram. Pulsed EPR spectroscopy allowed identifying the radical by analysis of the electron spin echo envelope modulation spectrum. The radical is localized on the carbon atom of the C=O-group of the N-methyl-2-pyrrolidone moiety with broken internal C-N bond of the lactam ring.

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

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

Bulletin of the Polish Academy of Sciences. Chemistry

2000

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.