Mono-, di- & trinuclear ternary complexes of Dy3+ & Tb3+ with pyrazole & oligo-diketonates are both luminescent and single molecule magnets. Quantum yields & Ueff values decrease with higher nuclearity & reduced intramolecular Ln–Ln distance.
A monomer-2-methyl-5-phenylpentene-1dione-3,5, its solvent metal complex Eu(III)-water, hybrid metal complex Eu(III)-phenanthroline, new metallopolymers based on them are obtained. The results of above studies have shown that the configuration of the chelate unit is unchanged during polymerization. Using the electron microscopy the homogeneity of metal distribution in the polymer matrix of synthesized metallopolymer was confirmed. The similarity of monomers electronic absorption spectra with polymers spectra confirms the identical coordinative environment of lanthanide ions in both cases. The solubilization of europium β-diketonate complexes with phenanthroline was shown to change luminescence intensity in such complexes.
As a continuation of studies of carbacylamidophosphate based coordination compounds a series of the lanthanide and yttrium complexes of general formula PPh4[LnL4], where Ln=La, Nd, Tb and Y; L– = [CCl3(CO)N(PO)(OCH3)2]– has been synthesized. The resulting compounds were characterized by means of thermal gravimetric analysis, IR, 1H NMR, UV-Vis absorption and luminescent spectroscopy. It was found, that each lanthanide ion of the [Ln(L)4]– complex anion is bonded to two oxygen atoms belonging to the phosphoryl and carboxyl groups of four bidentate chelated ligands, completing coordination number of lanthanide ion to eight. Analysis of signals integral intensity in the investigated NMR spectra of coordination compounds PPh4[LnL4] (Ln = La, Y) indicates the molar ratio of dimethyl-N-trichloroacetylamidophosphate ligand and tetraphenylphosphonium cation as 4:1, which corresponds to the proposed structure of the complexes. According to the absorption spectroscopy investigations data there is one type of lanthanide sites in the complexes. Low symmetry of lanthanide ion coordination environment was concluded from bands ratio in the europium complex luminescence spectrum. From the TGA analysis the stability of the coordination compounds till 160°C can be concluded. It was shown that tetraphenylphosphonium cation sensitizes europium ion emission and photo-excitation of PPh4[EuL4] complex by UV light results in red Eu3+ centered luminescence with dominating band of 5D0–7F2 transition in the spectrum and decay time equal one and a half millisecond.
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