Complexes of lanthanide nitrates with N,N-diethylantipyrine-4-carboxamide

New complexes of lanthanide nitrates with N, N-diethylantipyrine-4-carboxamide (DEAP), with the general formulae [Ln2(DEAP)3] [NO3]6 (where Ln = La, Pr, Nd, Sm, Tb, Ho, Er, Yb and Y) have been isolated and characterized by chemical analysis and various physical methods such as electrolytic conductance, IR and13C NMR spectral data. Electrolytic conductance values and infrared spectral studies indicate that the nitrate groups are coordinated. Infrared and13C NMR spectral analysis show that the ligand DEAP is coordinated to the tripositive metal ion through the diethylcarboxamide carbonyl and antipyrine carbonyl oxygens in a bidentate fashion.

Titania nanowires as substrates for sensing and photocatalysis of common textile industry effluents

Sensing and photocatalysis of textile industry effluents such as dyes using mesoporous anatase titania nanowires are discussed here.Spectroscopic investigations show that the titania nanowires preferentially sense cationic (e.g. Methylene Blue, Rhodamine B) over anionic (e.g. Orange G, Remazol Brilliant Blue R) dyes. The adsorbed dye concentration on titania nanowires increased with increase in nanowire dimensions and dye solution pH. Electrochemical sensing directly corroborated spectroscopic findings. Electrochemical detection sensitivity for Methylene Blue increased by more than two times in magnitude with tripling of nanowire average length. Photodegradation of Methylene Blue using titania nanowires is also more efficient than the commercial P25-TiO2 nanopowders. Keeping illumination protocol and observation times constant, the Methylene Blue concentration in solution decreased by only 50% in case of P25-TiO2 nanoparticles compared to a 100% decrease for titania nanowires. Photodegradation was also found to be function of exposure times and dye solution pH.Excellent sensing ability and photocatalytic activity of the titania nanowires is attributed to increased effective reaction area of the controlled nanostructured morphology. (C) 2010 Elsevier B.V. All rights reserved.

2,4-Lutidine-1-oxide complexes of lanthanide perchlorates

2,4-Lutidine-1-oxide (2,4-LutO) complexes of lanthanide perchlorates of the formulae Ln2(2,4-LutO)13(ClO4)6 (Ln = Pr and Nd) and Ln2(2,4-LutO)15 (ClO4)6 (Ln = La, Tb, Dy, Ho and Yb) have been prepared and characterised by chemical analysis, IR, NMR, conductance and electronic spectral data. Proton NMR data along with the IR data show that the ligand coordinates to the metal ion through the oxygen. Conductance data of the complexes in acetone and nitrobenzene indicate that the perchlorate is not coordinated to the metal ion.

Complexes of lanthanide nitrates with O,O′,N-triisopropyl phosphoramidate

A substituted phosphoramidate has been used as a ligand to lanthanides for the first time. New complexes of lanthanide nitrates with O,O′,N-triisopropyl phosphoramidate (TIP) of the general formula Ln(TIP)3(NO3)3 where Ln=La-Yb and Y have been synthesised and characterised by chemical analysis, infrared and visible electronic spectra and electrical conductance.Infrared spectra indicate the coordination of the ligand to the metal ions through the oxygen of the P=O group. IR and conductance show that the nitrate groups are all coordinated. Electronic spectral shapes have been interpreted in terms of an eight coordinate geometry around the metal ions.

Oxygen excess in layered lanthanide nickelates

Density measurements on large single-crystal specimens of La2NiO4+δ and Pr2NiO4+δ show that oxygen nonstoichiometry arises from the presence of excess lattice oxygen. X-ray photoelectron spectra as well as X-ray absorption edge studies provide no evidence for the existence of Ni3+ in these oxygen-excess nickelates under the conditions of the measurements. Transmission electron microscopy has revealed a novel type of exsolution process of the stoichiometric phase out of nonstoichiometric La2NiO4 during heating in CO2 at 870 K for 3 h. An interpretation of the results in terms of the existence of peroxide species within the conducting layers is proposed.

Amino acid-lanthanide interactions, Part 2. The X-ray crystal structures of lanthanide and calcium complexes of 1-amino-cyclohexane-1-carboxylic acid (Acc6)

The structures of [Nd-2(Acc(6))(H2O)(6)](ClO4)(6) .(H2O)(6) (1) [Er-2(Acc(6))(4)(H2O)(8)](ClO4)(6) .(H2O)(11) (2) and [Ca-5(Acc(6))(12)(H2O)(6)](ClO4)(10).(H2O)(4) (3) (Acc(6) = 1-aminocyclohexane-1-carboxylic acid) have been determined by X-ray crystallography. The lanthanide complexes 1 and 2 are dimeric in which two lanthanide cations are bridged by four carboxylato groups of Acc(6) molecules. In addition, the neodymium complex (1) features the unidentate coordination of the carboxyl group of an Acc(6) molecule in place of a water molecule in the erbium complex (2). The coordination number in both 1 and 2 is eight. The calcium Acc(6) complex (3) is polymeric; three different calcium environments are observed in the asymmetric unit. Two calcium ions are hexa-coordinated and one is hepta-coordinated. Considerable differences are observed between the solid state structures of Ln(III) and Ca-II complexes of Acc(6

A self-assembled, luminescent europium cholate hydrogel: a novel approach towards lanthanide sensitization

We propose a new self-assembly based strategy for the design of novel lanthanide based luminescent materials. In this approach a europium hydrogel is prepared and sensitization is achieved by doping the gel with pyrene in a non-coordinated fashion.

Lanthanide perchlorate complexes of o,o' diisopropyl, n(-4-antipyryl) phosphoramidate

Five new complexes of lanthanide perchlorates with a new ligand O,O' diisopropyl N(-4-antipyryl) phosphoramidate (DIAP) of the general formula Ln(DIAP)4(ClO4)3 where Ln = La, Pr, Nd, Sm and Gd, have been synthesised and characterized by chemical analysis, IR(200–4000cm−1) and electronic spectra and electrical conductance data. Infrared spectral data indicate the coordination of the ligand to the metal ions in a bidentate fashion, through the C=O oxygen of the antipyrine group and the P=O group. IR and conductance values show that the three perchlorate groups are ionic. Electronic spectrum of the Nd3+ complex in the visible region, indicates reasonable covalency in the metal-ligand bond. The available data point to an eight coordinate geometry around the metal ions, with each ligand behaving in a bidentate ‘00’ fashion.

4-Nitro 2-picoline-l-oxide complexes of lanthanide perchlorates

4-Nitro 2-picoline-l-oxide (NPicO) complexes of the formulae La (NPicO)5 (CIO4)3, Ln2 (NPicO)9 (C1O4)6 (Ln = Pr, Nd, and Gd) and Ln (NPicO)4 (CIO4)3 (Ln == Tb, Dy, Ho and Yb) have been synthesised and characterised by analysis, electrolytic conductance, infrared, proton NMR and electronic spectral data. A tentative coordination number of 6 for all the complexes have been assigned

Citrate gel processing of the perovskite lanthanide chromites

Chemically pure and stoichiometric lanthanide chromites, LnCrO3, where Ln = La, Pr, Nd, Sm, Gd, Dy, Ho, Yb, Lu and YCrO3 have been prepared by the calcination of the corresponding lanthanide bis(citrato)chromium {Ln[Cr(C6H5O7)2·nH2O} complexes at relatively low temperatures. Formation of the chromites was confirmed by powder X-ray diffraction, infrared and electronic spectra. The citrate gel process is found to be highly economical, time-saving and appropriate for the large-scale production of these ceramic materials at low temperatures compared with other non-conventional methods.

Low-temperature preparation and characterization of phase-pure lanthanide chromates (V) by the citrate gel process

Phase-pure, crystalline lanthanide chromates LnCrO4 (V), where Ln = La, Pr, Nd, Sm, Gd, Dy, Ho, Yb, Lu and Y, have been prepared by the controlled combustion of the corresponding lanthanide biscitrato chromium (III) complexes at comparatively low temperatures. Formation of chromates (V) was confirmed by X-ray diffraction, infrared and electronic spectroscopy. Phase purity of the materials has also been confirmed by X-ray photoelectron spectroscopy.

Lanthanide Luminescent Coordination Polymer Constructed from Unsymmetrical Dinuclear Building Blocks Based on 4-((1H-Benzod]imidazol-1-yl)methyl)benzoic Acid

Lanthanide coordination polymers of the general formula Ln(2)(L)(5)(NO3)(H2O)(4)](n) (Ln = Eu (1), Tb (2), Gd (3)) supported by a novel aromatic carboxylate ligand 4-((1H-benzod]imidazol-1-yl)methyl)benzoic acid (HL) have been synthesized, characterized, and their photoluminescence behavior is examined. The powder X-ray diffraction patterns of complexes 1-3 showed that 1-3 are isostructural; thus, 1 has been chosen as an example to discuss in detail about the molecular structure by single-crystal X-ray diffraction. Complex 1 is a one-dimensional (1D) helical chain-like coordination polymer consisting of unique unsymmetrical dinuclear lanthanide building blocks. The 1D chains are further linked by the significant intermolecular hydrogen-bonding interactions to form a two-dimensional supramolecular network. The Tb3+ complex exhibits bright green luminescence efficiency in the solid state with a quantum yield of 15%. On the other hand, poor luminescence efficiency has been noted for Eu3+-benzoate complex.

Lanthanide Sulfate Frameworks: Synthesis, Structure, and Optical Properties

Layered lanthanide sulfate compounds with three different structures have been prepared and characterized. The compounds C10H10N2] La(SO4)(2)]center dot 2H(2)O (I), C10H10N2] La(SO4)(2)(H2O)(2)](2) (Ha), C10H10N2]Pr(SO4)(2)(H2O)(2)](2) (IIb), C10H10N2]Nd-2(SO4)(4)(H2O)(2)](2) (IIIa), C10H10N2]Sm-2(SO4)(4)(H2O)(2)](2) (IIIb), and C10H10N2]Eu-2(SO4)(4)(H2O)(2)] 2 (IIIC) have anionic lanthanide sulfate layers separated by protonated bipyridine molecules. The layers are formed by the connectivity between the lanthanide polyhedra and sulfate tetrahedra. The formation of a two-dimensional La-O-La layer (la), Pr-O-Pr chains (IIb), and a tetramer cluster (IIIa) is noteworthy. The compounds exhibit honeycomb (I), square (IIa, IIb), and honeycomb (IIIa-IIIc) net arrangements, when the connectivity between the lanthanide ions is considered. Optical studies indicate the observation of characteristic metal-centered emission at room temperature. The Nd compound (IIIa) exhibits a two-photon upconversion behavior.