Roman V. Rumyantcev

Substituted naphtholates of rare earth metals as emissive materials

The synthesis, characterization, photoluminescent (PL) and electroluminescent (EL) behavior of trivalent Sc, Nd, Gd, Er, Tm and Yb complexes with 3-(5-methylbenzoxazol-2-yl)naphthol (L-5Me) and 3-(6-methylbenzoxazol-2-yl)naphthol (L-6Me) ligands are reported. An X-ray analysis of Sc(L-5Me)3, Sc(L-6Me)3 as well as the non-methylated analogue Sc(L)3 has shown the monomeric structure of the complexes whereas the lanthanide naphtholates according to LDI-TOF data are dimers Ln2(L-5Me)6 and Ln2(L-6Me)6. The scandium complexes under photo- and electroexcitation revealed intense ligand-centered luminescence peaked at 522 nm. The PL and EL spectra of Nd, Tm and Yb compounds displayed moderate ligand-centered emission along with narrow bands of corresponding f–f transitions.

Valence–Tautomeric Interconversion in a Bis(dioxolene)cobalt Complex with Iminopyridine Functionalized by a TEMPO Moiety. Phase Transition Coupled with Monocrystal Destruction

Iminopyridine modified by TEMPO nitroxide was utilized for the synthesis of an octahedral bis(o-semiquinonato)cobalt complex. Variable-temperature magnetic susceptibility measurements detect a valence tautomeric transformation in the temperature range 200-300 K. A reproducible hysteresis loop of about 40 K width is observed on the magnetic moment temperature dependence in the transition region. Differential scanning calorimetry measurements confirm different temperatures of phase transitions accompanying a valence-tautomeric transformation upon heating and cooling. Attempts to study the structural changes associated with the valence-tautomeric transformation by single-crystal X-ray diffraction failed because of the crystal destruction taking place upon cooling from 220 K. The powder X-ray diffraction pattern indicated an essential change of the unit cell upon cooling from 240 K.