Praseodymium Metallacrown-Based NMR Probe for Enantioselective Discrimination of Mandelate Anions in Water.

Recently, the enhanced interest in water-soluble aminohydroximate Ln(III)-Cu(II) metallacrowns (MC) is largely due to their fascinating structural chemistry, diverse properties and ease of synthesis. We examined the water-soluble praseodymium(III) alaninehydroximate complex Pr(H2O)4[15-MCCu(II)Alaha-5]·3Cl (1) as a highly effective chiral lanthanide shift reagent for NMR analysis of the biologically relevant (R/S)-mandelate (MA) anions in aqueous media. The R-MA and S-MA enantiomers can be easily discriminated in the presence of small (1.2-6.2 mol %) amounts of MC 1 by the 1H NMR signals of multiple protons exhibiting an enantiomeric shift difference (ΔΔδ) of 0.06 ppm up to 0.31 ppm. Additionally, a possibility of coordination of MA to the metallacrown was investigated by the ESI-MS technique and a Density Functional Theory modeling of the molecular electrostatic potential and noncovalent interactions.

Water-Soluble Bismuth(III) Polynuclear Tyrosinehydroximate Metallamacrocyclic Complex: Structural Parallels to Lanthanide Metallacrowns.

Recently there has been a great deal of interest and associated research into aspects of the coordination chemistry of lanthanides and bismuth-elements that show intriguing common features. This work focuses on the synthesis and characterization of a novel bismuth(III) polynuclear metallamacrocyclic complex derived from aminohydroxamic acid, in order to compare the coordination ability of Bi3+ with the similarly sized La3+ ions. A polynuclear tyrosinehydroximate Bi(OH)[15-MCCu(II)Tyrha-5](NO3)2 (1) was obtained according to the synthetic routes previously described for water-soluble Ln(III)-Cu(II) 15-MC-5 metallacrowns. Correlations between structural parameters of Bi(III) and Ln(III) complexes were analyzed. DFT calculations confirmed the similarity between molecular structures of the model bismuth(III) and lanthanum(III) tyrosinehydroximate 15-metallacrowns-5. Analysis of the electronic structures revealed, however, stronger donor-acceptor interactions between the central ion and the metallamacrocycle in the case of the lanthanum analogue. Thermochromic properties of 1 were studied.

The first water-soluble polynuclear metallamacrocyclic Sr(ii)-Cu(ii) complex based on simple glycinehydroximate ligands.

Recently, aminohydroximate ligands have found wide applications in the fascinating class of polynuclear metallamacrocyclic compounds named 15-MC-5 metallacrowns. The enhanced interest in water-soluble aminohydroximate Ln(iii)-Cu(ii) complexes is largely due to their rich coordination chemistry, diverse properties and ease of synthesis. We examined glycinehydroxamic acid as a simple ligand for the preparation of the first water-soluble polynuclear metallamacrocyclic Sr(ii)-Cu(ii) compound. The complex Sr(H2O)3[15-MCCuGlyha-5](Cl)2 was synthesized and characterized structurally and spectroscopically. The single-crystal structure reveals the classic metallamacrocyclic 15-MC-5 configuration. The Sr(ii) ion is located at the center of the 15-MCCu(II)Glyha-5 ring and coordinated by five oxygen atoms of the cycle in the equatorial plane and an additional three oxygen atoms of the water molecules at apical positions. Detailed DFT and QT AIM studies were carried out for the hydrated isoelectronic Sr[15-MCCuGlyha-5]2+ and Y[15-MCCuGlyha-5]3+ systems. The ionic contribution to the metal-ligand interactions appears to be higher for the Sr(ii) derivative despite the smaller charge separation. DFT calculations suggest a thermodynamically favorable substitution of the Sr(ii) central ion with Y(iii). Indeed, it was shown experimentally that the strontium ion can be easily replaced by yttrium. Preliminary cytotoxic studies revealed the low toxicity of the strontium complex and its yttrium analogue, so the water-soluble Sr(ii) and Y(iii) metallacrowns can be further investigated as possible platforms for the development of new 90Sr and 90Y radiotherapy drugs.

Anhydrous mono- and dinuclear tris(quinolinolate) complexes of scandium: the missing structures of rare earth metal 8-quinolinolates.

The first monomeric anhydrous scandium tris(8-quinolinolate) complex 1 with the 2-amino-8-quinolinolate ligands and the Sc(2)Q(6) dinuclear complex 2 with the unsubstituted 8-quinolinolate ligands have been synthesized and characterized by X-ray analysis and DFT calculations. The intramolecular hydrogen bonds appear to be responsible for the unique monomeric structure of complex 1. The DFT-based analysis of the electron density topology reveals the (3,-1) critical points corresponding to the O···H and N···H bonds. The two scandium atoms in compound 2 are inequivalent due to different ligand surroundings. They are coordinated by seven (5O, 2N) and eight (4O, 4N) ligand atoms. The increase in the coordination number is accompanied by a decrease in the positive charge of the metal atom as evidenced by the DFT calculations.

New trends in design of electroluminescent rare earth metallo-complexes for OLEDs.

The metal-organic complexes of Sc, Y, La and lanthanides, which were tested as luminescent materials in organic light emitting diodes (OLEDs), are collected. The performances of the devices are given. Advantages and drawbacks of organic derivatives of rare earth metals as emissive materials are considered.

Synthesis, structures, and electroluminescent properties of scandium N,O-chelated complexes toward near-white organic light-emitting diodes.

Three members of a new class of electroluminescent, neutral, and monomeric scandium N,O-chelate complexes, namely, Sc(III)-tris-2-(2-benzoimidazol-2-yl)phenolate (1), Sc(III)-tris-2-(2-benzoxyazol-2-yl)phenolate (2), and Sc(III)-tris-2-(2-benzothiazol-2-yl)phenolate (3), have been prepared and X-ray characterized. DFT calculations have been performed. In contrast to the most frequently applied dual or multiple dopants in multilayer white OLED devices, all our simpler devices with the configuration of indium tin oxide/N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine/neat scandium complex/Yb exhibit close to near-white emission with a blue hue (CIE(x,y) = 0.2147, 0.2379) in the case of 1, a cyan hue (0.2702, 0.3524) in the case of 2, and a yellowish hue (0.3468; 0.4284) in the case of 3.