N. P. Kuz’mina

Photo and electroluminescence of lanthanide(III) complexes

Major classes of coordination compounds used as electroluminescent materials are surveyed, and their advantages and disadvantages are discussed. The strategy of the directed synthesis of lanthanide(III) complexes promising for use as electroluminescent materials is formulated. The results of studies dealing with the design of electroluminescent devices based on europium(III), terbium(III), and thulium(III) complexes are considered.

Influence of heteroligand complexation on the thermal, photoluminescent, and film-forming properties of some aromatic terbium(III) carboxylates

With homoligand TbL3 and heteroligand complexes TbL3(Q)n (HL = HSal (salicylic acid) and HPA (2-anilinobenzoic acid); Q = TPPO (triphenylphosphine oxide) and TOPO (tri(n-octyl)phosphine oxide); n = 1 or 2) as examples, it was shown that heteroligand complexation affects not only the thermal and photoluminescent properties but also the quality of films obtained by centrifugation: the root-mean-square roughness changes in the order TbL3Q > TbL3(Q)2 ≈ TbL3. This is due to different association degrees of the complexes in solution, which was confirmed by MALDI-TOF MS data.

Photo- and electroluminescent properties of zinc(II) complexes with tetradentate Schiff bases, derivatives of salicylic aldehyde

It is studied how the introduction of various substituents into the composition of organic ligands affects the photoluminescence spectra of new zinc(II) complexes with tetradentate Schiff bases H2L (derivatives of salicylic aldehyde (H2SAL1, H2SAL2) and o-vanillin (H2MO1, H2MO2) with ethylenediamine and o-phenylenediamine) in the form of bulk solids and thin films. It is demonstrated that the emission spectra of bulk solid complexes without o-phenylenediamine bridges (ZnSAL1 and ZnMO1) contain additional long-wavelength bands compared to the spectra of corresponding thin films. In the case of films obtained from [ZnSAL1]2 dimer complexes, the long-wavelength band is dominant. At the same time, the photoluminescence spectra of ZnSAL2 and ZnMO2 complexes with o-phenylenediamine bridges are similar in the case of solid samples and thin films. The electroluminescent properties of organic light-emitting diodes (OLEDs) with the ITO/α-NPD/ZnL/Ca:Al structure are studied. The bathochromic shift of the electroluminescence peaks of OLEDs with respect to the photoluminescence spectra of bulk solid samples and thin films is probably related to the formation of exciplexes at the α-NPD/ZnL interface. The electroluminescence spectra of OLEDs based on [ZnSAL1]2 show a hypsochromic shift of the emission maximum, which can be caused by a shift of the recombination region into the α-NPD layer.

Gas-Phase Synthesis of Lanthanide(III) Benzoates Ln(Bz) 3 (Ln = La, Tb, Lu)

A new method for the synthesis and film deposition of nonvolatile aromatic lanthanide(III) carboxylates by ligand exchange reaction between the starting volatile components in the gas phase was proposed. The complexes Ln(Bz)3 (Ln = La3+, Tb3+, Lu3+, HBz = benzoic acid) were synthesized by gas-phase ligand exchange reaction between the volatile Ln(Thd)3 and HBz (HThd = 2,2,6,6-tetramethylheptane-3,5-dione). The composition of the complexes was confirmed by elemental, thermal, IR-spectroscopic, and photoluminescence analyses and, in the case of lanthanum and lutetium complexes, by 1H NMR.

Gas-phase synthesis of terbium and lutetium carboxylates

Gas-phase ligand exchange between volatile lanthanide dipivaloylmethanates (Ln(dpm)3; Hdpm is dipivaloylmethane, Ln = Tb, Lu) and o-substituted aromatic carboxylic acids (HCarb = Hsal is o-hydroxybenzoic acid, Habz is o-aminobenzoic acid, Hpobz is o-phenoxybenzoic acid, Hpa is o-anilinobenzoic acid). The gas-phase reaction involves the formation of the mixed-ligand complex Ln (dpm)3−n(Carb)n, which is subsequently converted into tris-carboxylate (Ln(Carb)3) on heating of the product in vacuum.

IR Spectra of N,N′-Ethylene-Bis(salicylaldiminates) and N,N′-ethylene-Bis(acetylacetoniminates) of Ni(II), Cu(II), and Zn(II)

Vibrational spectra of N,N′-ethylene-Bis(salicylaldiminaates) and N,N′-ethylene-Bis(acetylacetoniminates) of nickel (II), copper (II), and zinc (II) are studied experimentally (IR spectroscopy, 400–4000 cm−1) and theoretically (B3LYP), band assignment is given, and the distribution of potential energy of normal vibrations in internal coordinates is studied. Differences between vibrational spectra of the complexes are discussed. Thermodynamic functions of gas-phase complexes corresponding to temperatures of 298 and 800 K are calculated.

Yttrium tris-propionate monohydrate: Synthesis, crystal structure, and thermal stability

The complex [Y(Prop)3(H2O)]∞ (I) was prepared by treating yttrium carbonate, acetate, or acetylacetonate hydrates with propionic acid and characterized by the data of elemental analysis, IR spectroscopy, X-ray diffraction, and thermal analysis in air. Complex I has a polymeric layered structure with clear-cut structure-forming dimeric groups bridged by bidentate ligands. Only van der Waals interactions occur between the adjacent polymeric layers. In air, yttrium propionate monohydrate I is completely converted to the oxide at 600°C.

A mass spectrometric study of the vaporization of erbium hexafluoroacetylacetonate

The sublimation of erbium tris-hexafluoroacetylacetonate Er(C5O2HF6)3 was studied by the Knudsen effusion method with the mass spectrometric determination of vapor composition. Groups of ions containing one, two, and three metal atoms were recorded. The enthalpies of sublimation of the monomeric, dimeric, and trimeric forms ΔSH°(362 K) were found to be 133 ± 4, 135 ± 7, and 139 ± 38 kJ/mol, respectively. The melting point of Er(C5O2HF6)3 was 390 ± 2 K. No oligomeric forms were observed in vapor superheated above 430 K.

Ytterbium tris(hexafluoroacetylacetonate) Yb(C5O2HF6)3: The composition of overheated vapor and sublimation thermodynamics

A mass spectrometric study of the saturated vapor over ytterbium tris(hexafluoroacetylacetonate) Yb(hfa)3 (hfa = CF3-C(O)-CH-C(O)-CF3) and of the vapor overheated up to the thermal decomposition temperature of the complex is presented. The vapor composition changes markedly with increasing temperature. At T ≈ 370 K, the mass spectrum of the vapor over Yb(hfa)3 indicates the presence of ions containing one to three metal atoms. As the temperature is raised, the ion currents due to oligomer ions decrease. The oligomers are not detected at T > 440 K. The total decomposition temperature of Yb(hfa)3 is 663(9) K. The second-law enthalpy of sublimation (ΔHso (380 K)) is 134 ± 7 kJ/mol for the monomer and 138 ± 10 kJ/mol for the dimer. The enthalpy of dissociation of the dimer into monomer molecules is nearly equal to the enthalpy of sublimation of the monomer and dimer: ΔHdis(380 K) = 130 ± 15 kJ/mol.

Mass spectrometric study of the overheated vapor over Ni(II), Cu(II), and Zn(II) N,N′-ethylenebis(acetylacetoniminato) complexes

A mass spectrometric study of the overheated vapor over the complexes Ni(acacen), Cu(acacen), and Zn(acacen) (H2acacen = N,N′-ethylenebis(acetylacetonimine)) has been carried out in the temperature range of 180–760°C. Irrespective of the degree of overheating, the vapor phases over all of these compounds contain no ions heavier than the molecular ion [MO2N2C12H18]+. The existence of molecular ions in the overheated vapor in the double-chamber two-temperature effusion cell is evidence of the high thermal stability of the complexes. The onset temperature of the thermal decomposition of Ni(acacen), Cu(acacen), and Zn(acacen) is 690, 610, and 560°C, respectively. The way of fragmentation of the chelates under electron impact ionization depends on the nature of the metal.