13813-24-6Relevant academic research and scientific papers
Intense near-infrared luminescence of anhydrous lanthanide(III) iodides in an imidazolium ionic liquid
Arenz, Sven,Babai, Arash,Binnemans, Koen,Driesen, Kris,Giernoth, Ralf,Mudring, Anja-Verena,Nockemann, Peter
, p. 75 - 79 (2005)
Anhydrous neodymium(III) iodide and erbium(III) iodide were dissolved in carefully dried batches of the ionic liquid 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C12mim][Tf2N]. Provided that the ionic liquid had a low water content, intense near-infrared emission could be observed for both the neodymium(III) ion and for the erbium(III) ion. Luminescence lifetimes have been measured, and the quantum yield of the neodymium(III) sample has been measured. Exposure of the hygroscopic samples to atmospheric moisture conditions caused a rapid decrease of the luminescence intensities.
Lanthanide iodides as promoters of acetonitrile amination. Molecular structure of MeC({double bond, long}NH)NHPri, MeC({double bond, long}NH)NHBut and {Dy[MeC({double bond, long}NH)NEt2]6}I3
Bochkarev, Mikhail N.,Balashova, Tatyana V.,Maleev, Alexander A.,Fagin, Anatolii A.,Fukin, Georgy K.,Baranov, Evgenii V.
, p. 2368 - 2378 (2007)
Amination of acetonitrile by the amines MeNH2, PrnNH2, PriNH2, ButNH2, and Et2NH is efficiently promoted by the lanthanide iodides LnI2 (Ln = Nd, Dy, Tm), LnI3 (Ln = Pr, Nd, Dy) and LnI3(THF)3 (Ln = Pr, Nd, Dy). The formed mono- and N,N′-disubstituted amidines MeC({double bond, long}NH)NHR (R = Pri, But), MeC({double bond, long}NH)NEt2, MeC({double bond, long}NR)NHR (R = Me, Prn) were isolated mainly as the complexes with starting iodide of general composition LnI2(amidine)x (1) or LnI3(amidine)x (2) (x = 3-8). In the products 1, which evidently are the mixtures of LnI2+, LnI2+ and LnI3 derivatives, the metal exists in trivalent state but one of the ligands actually is amidinate anion. A part of the generated amidines remains in the reaction solutions in free form. Heating of the 1 and 2 in vacuum at 150-200 °C affords corresponding amidine and the complexes with reduced amount of the amidine ligands LnI2(amidine)y (3) or LnI3(amidine)y (4) (y = 2-3). The products 3 and 4 displayed the same catalytic activity in the acetonitrile-amine cross-coupling as the initial iodides. SmI2 and especially YbI2 revealed lower activity. The structure of isopropylacetamidine (5), tert-butylacetamidine (6) and {Dy[MeC({double bond, long}NH)NEt2]6}I3(MeCN) (7) were determined by X-ray diffraction analysis.
Strong luminescence of rare earth compounds in ionic liquids: Luminescent properties of lanthanide(III) iodides in the ionic liquid 1-dodecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide
Mudring, Anja-Verena,Babai, Arash,Arenz, Sven,Giernoth, Ralf,Binnemans,Driesen, Kris,Nockemann, Peter
, p. 204 - 208 (2006)
Purposely designed ionic liquids can be excellent solvents for spectroscopic studies of rare earth compounds. Absorption, excitation and emission spectra of LnI3 (Ln = Nd, Dy and Tb) in the ionic liquid 1-dodecyl-3-methylimidazolium bis(trifluo
Accessing lanthanide diiodide reactivity for coupling alkyl chlorides to carbonyl compounds via the NdI3/ alkali metal reduction system
Evans, William J.,Workman, Penny S.
, p. 1989 - 1991 (2005)
The combination of NdI3 and a reducing agent such as KC 8, K, Na, or Ca can mimic the reductive chemistry of NdI2 in coupling of alkyl and allyl chlorides with carbonyl compounds.
Structural characterization of methanol substituted lanthanum halides
Boyle, Timothy J.,Ottley, Leigh Anna M.,Alam, Todd M.,Rodriguez, Mark A.,Yang, Pin,Mcintyre, Sarah K.
, p. 1784 - 1795 (2010/07/03)
The first study into the alcohol solvation of lanthanum halide [LaX3] derivatives as a means to lower the processing temperature for the production of the LaBr3 scintillators was undertaken using methanol (MeOH). Initially the de-hydration of {[La(μ-Br)(H2O)7](Br)2}2 (1) was investigated through the simple room temperature dissolution of 1 in MeOH. The mixed solvate monomeric [La(H2O)7(MeOH)2](Br)3 (2) compound was isolated where the La metal center retains its original 9-coordination through the binding of two additional MeOH solvents but necessitates the transfer of the innersphere Br to the outersphere. In an attempt to in situ dry the reaction mixture of 1 in MeOH over CaH2, crystals of [Ca(MeOH)6](Br)2 (3) were isolated. Compound 1 dissolved in MeOH at reflux temperatures led to the isolation of an unusual arrangement identified as the salt derivative {[LaBr2.75·5.25(MeOH)]+0.25 [LaBr3.25·4.75(MeOH)]-0.25} (4). The fully substituted species was ultimately isolated through the dissolution of dried LaBr3 in MeOH forming the 8-coordinated [LaBr3(MeOH)5] (5) complex. It was determined that the concentration of the crystallization solution directed the structure isolated (4 concentrated; 5 dilute) The other LaX3 derivatives were isolated as [(MeOH)4(Cl)2La(μ-Cl)]2 (6) and [La(MeOH)9](I)3·MeOH (7). Beryllium Dome XRD analysis indicated that the bulk material for 5 appear to have multiple solvated species, 6 is consistent with the single crystal, and 7 was too broad to elucidate structural aspects. Multinuclear NMR (139La) indicated that these compounds do not retain their structure in MeOD. TGA/DTA data revealed that the de-solvation temperatures of the MeOH derivatives 4-6 were slightly higher in comparison to their hydrated counterparts.
Lanthanide(III) halides: Thermodynamic properties and their correlation with crystal structure
Rycerz,Gaune-Escard
, p. 167 - 174 (2008/10/09)
Temperatures and enthalpies of phase transitions of 17 lanthanide(III) halides determined experimentally are reported. Correlations were made between temperature of fusion of lanthanide(III) halides, on the one hand, and enthalpy of fusion, on the other, versus atomic number of lanthanide. According to this classification, the lanthanide(III) halides split into groups, as also do the corresponding crystal structures. A correlation between the crystal structure of lanthanide(III) halides and their respective entropy of fusion (or entropy of fusion + entropy of solid-solid phase transition) was inferred from the aforementioned features. Fusion in those halides with hexagonal, UCl3-type and orthorhombic, PuBr3-type, structures entails an entropy of fusion change (or entropy of fusion + entropy of solid-solid phase transition change) by 50 ± 4 J mol-1 K-1. The homologous entropy change within the group of halides having the rhomboedric, FeCl3-type, structure, is smaller and equals 40 ± 4 J mol-1 K-1. Halides with monoclinic, AlCl3-type, crystal structure constitute a third group associated to an even smaller entropy change upon fusion, only 31 ± 4 J mol-1 K-1. The halides with lower entropies of fusion also have a lower S1300 K - S298 K indicating either a higher degree of order in the liquid or a higher entropy in the solid at room temperatures.
The extended chain compounds Ln12(C2)3I17 (Ln=Pr, Nd, Gd, Dy): Synthesis, structure and physical properties
Ryazanov, Mikhail,Mattausch, Hansjuergen,Simon, Arndt
, p. 1372 - 1380 (2008/10/09)
The title compounds are obtained in high yield from stoichiometric mixtures of Ln, LnI3 and graphite, heated at 900-950 °C in welded Ta containers. The crystal structures of new Pr and Nd phases determined by single-crystal X-ray diffraction are related to those of other Ln12(C2)3I17-type compounds (C 2/c, a=19.610(1) and 19.574(4) A, b=12.406(2) and 12.393(3) A, c=19.062(5) and 19.003(5) A, β=90.45(3)° and 90.41(3)°, for Pr12(C2)3I17 and Nd12(C2)3I17, respectively). All compounds contain infinite zigzag chains of C2-centered metal atom octahedra condensed by edge-sharing into the [tcc]∞ sequence (c=cis, t=trans) and surrounded by edge-bridging iodine atoms as well as by apical iodine atoms that bridge between chains. The polycrystalline Gd12(C2)3I17 sample exhibits semiconducting thermal behavior which is consistent with an ionic formulation (Ln3+)12(C26-)3(I-)17(e-) under the assumption that one extra electron is localized in metal-metal bonding. The magnetization measurements on Nd12(C2)3I17, Gd12(C2)3I17 and Dy12(C2)3I17 indicate the coexistence of competing magnetic interactions leading to spin freezing at Tf=5 K for the Gd phase. The Nd and Dy compounds order antiferromagnetically at TN=25 and 29 K, respectively. For Dy12(C2)3I17, a metamagnetic transition is observed at a critical magnetic field H≈25 kOe.
Chemiluminescence in the reaction of LnI2 (Ln = Dy, Nd) with water
Bulgakov,Kuleshov,Kinzyabaeva,Fagin,Masalimov,Bochkarev
, p. 1956 - 1959 (2008/09/18)
Chemiluminescence (CL) upon the reaction of crystalline LnI2 (Ln = Dy, Nd) with water was found. The CL emitters are the Ln3+* electron-excited ions (Dy3+*, λmax = 470, 570 nm; Nd3+*, λ = 700-1200 nm)
Specific chemical behavior of NdII and DyII iodides in reactions with aromatic compounds
Bochkarev,Fagin,Khoroshenkov
, p. 1909 - 1914 (2007/10/03)
Benzene, toluene, tert-butylbenzene, or biphenyl virtually do not react with NdI2 (1) or DyI2 (2) in THF at -20°C but appreciably accelerate the reactions of these salts with solvents, resulting in LnI3 and intractable mixtures of products of the general composition [LnI(H)(R)(THF)] (R are fragments of the THF molecule). The same effect is induced by the addition of diphenylmercury or tetraphenyltin to solutions of 1 or 2. Phenol easily oxidizes 1 and 2 to give at 0°C the PhOLnI 2(THF)x complexes (x = 3, 4) in 55-95% yields. At -90°C, iodide 2 is converted into a similar complex PhODyI 2(THF)4, whereas 1 gives a mixture of PhONdI 2(THF)4, (PhO)2NdI(THF)5, NdI 3(THF)3, and [NdI(H)R(THF)]. A plausible pathway of the reactions including the intermediate formation of extremely reactive monovalent lanthanide iodides LnI is discussed.
Thermal decomposition and solution calorimetry of ammonium neodymium iodides
Hennig,Oppermann
, p. 65 - 73 (2007/10/03)
The thermodynamical data of ammonium neodymium iodides (NH4)3NdI6 and (NH4)2NdIs were derived by the determination of their decomposition equilibria by total pressure measurements. Moreover
