Observation of Slow Magnetic Relaxation in Discrete Dysprosium Cubane

A discrete dysprosium cubane has been prepared and structurally characterized Slow relaxation of magnetization in this complex is observed, which may stimulate further investigations into the dynamics of magnetization in lanthanide clusters with different topologies.

Interactions of Rare Earth-Amino Acid Complexes with Nucleic Acids

A number of metal-based anticancer drugs are designed to target nucleic acids. Therefore, the elucidation of their interactions with nucleic acids is important for rational design of new anticancer agents with high selectivity and low toxicity, which has been received much attention in this field. Lanthanide complexes have the potential to be therapeutic agents due to their unique magnetic, optical, electronic, and coordinate characteristics. However, lanthanide ions are easy to hydrolysis under physiological pH, which makes it difficult to study rare earth complexes nucleic acids selectivity. Recent studies have shown that natural amino acids can form stable complexes with rare earth ions under near physiological condition and the complexes have high solubility. This review summarizes the current progress in rare earth-amino acid complexes binding to nuclelic acids and their selectivity.

Bifunctional magnetic-optical nanocomposites: Grafting lanthanide complex onto core-shell magnetic silica nanoarchitecture

Anew class of bifunctional architecture combining the useful functions of superparamagnetism and terbium complex luminescence into one material has been prepared via two main steps by a modified Stober method and the layer-by-layer (LbL) assembly technique. The obtained bifunctional nanocomposites exhibit superparamagnetic behavior, high fluorescence intensity, and color purity. The architecture has been characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), UV-vis absorption and emission spectroscopy, X-ray diffraction, and superconducting quantum interference device (SQUID) magnetometry.

Synthesis, structure, photoluminescence, and electroluminescence properties of a new dysprosium complex

A new dysprosium complex Dy(PM)(3)(TP)(2) [where PM = 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone and TP = triphenyl phosphine oxide] was synthesized, and its single-crystal structure was also studied. Its photophysical properties were studied by absorption spectra, emission spectra, fluorescence quantum efficiency, and decay time of the f-f transition of the Dy3+ ion. In addition, the antenna effect was introduced to discuss the energy transfer mechanism between the ligand and the central Dy3+ ion. Finally, a series of devices with various structures was fabricated to investigate the electroluminescence (EL) performances of Dy(PM)(3)(TP)(2). The best device with the structure ITO/CuPc 15 nm/Dy complex 70 nm/BCP 20 nm/AlQ 30 nm/LiF 1 nm/Al 100 nm exhibits a maximum brightness of 524 cd/m(2), a current efficiency of 0.73 cd/A, and a power efficiency of 0.16 lm/W, which means that a great improvement in the performances of the device was obtained as compared to the results reported in published literature. Being identical to the PL spectrum, the EL spectrum of the complex also shows characteristic emissions of the Dy3+ ion, which consist of a yellow band at 572 nm and a blue emission band at 480 nm corresponding to the F-4(9/2)-H-6(13/2) and F-4(9/2)-H-6(15/2) transition of the Dy3+ ion, respectively. Consequently, an appropriate tuning of the blue/yellow intensity ratio can be presumed to accomplish a white luminescent emission.

Near-infrared luminescent mesoporous materials covalently bonded with ternary lanthanide [Er(III), Nd(III), Yb(III), Sm(III), Pr(III)] complexes

New near-infrared-luminescent mesoporous materials were prepared by linking ternary lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) complexes to the ordered mesoporous MCM-41 through a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline. The resulting materials (denoted as Ln(hfth)(3)phen-M41 and Pr(tfnb)(3)phen-M41; Ln=Er, Yb, Nd, Sm; hfth = 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate; tfnb = 4,4,4-trifluoro-1-(2-naphthyl)- 1, 3-butanedionate) were characterized by powder X-ray diffraction, N-2 adsorption/desorption, and elemental analysis. Luminescence spectra of these lanthanide-complex functionalized materials were recorded, and the luminescence decay times were measured. Upon excitation at the absorption of the organic ligands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) ions by sensitization from the organic ligands moiety. The good luminescent performances enable these NIR-luminescent mesoporous materials to have possible applications in optical amplification (operating at 1300 or 1500 nm), laser systems, or medical diagnostics.

Investigation on relationship between charge transfer position and dielectric definition of average energy gap in Eu3+-doped compounds

The dielectric definition of average energy gap E-g of the chemical bond has been calculated quantitatively in Eu3+-doped 30 lanthanide compounds based on the dielectric theory of chemical bond for complex structure crystals. The relationship between the experimental charge transfer (CT) energy of Eu3+ and the corresponding average energy gap E-g has been studied. The results show that the CT energy increases linearly with increasing of the average energy gap E-g. The linear model is obtained. It allows us to predict the CT position of Eu3+-doped lanthanide compounds with knowledge of the crystal structure and index of refraction. Applied to the Ca4GdO(BO3)(3):Eu and Li2Lu5O4(BO3)(3):Eu crystals, the predicted results of CT energies are in good agreement with the experimental values, and it can be concluded that the lowest CT energy in Li2Lu5O4(BO3)(3):Eu originates from the site of Lu1.

Rare earth metal alkyl complexes bearing N,O,P multidentate ligands: Synthesis, characterization and catalysis on the ring-opening polymerization of L-lactide

Alkane elimination reactions of rare earth metal tris(alkyl)s, Ln(CH2SiMe3)3(THF)2 (Ln = Y, Lu) with the multidentate ligands HL1-4, afforded a series of new rare earth metal complexes. Yttrium, complex I supported by flexible amino-intino phenoxide ligand HL1 was isolated as homoleptic product. In the reaction of rigid phosphino-imino phenoxide ligand HL 2 with equintolar Ln(CH2SiMe3)3(THF)2, HL 2 was deprotonated by the metal alkyl and its imino C=N group was reduced to C-N by intramolecular alkylation, generating THF-solvated mono-alkyl complexes (2a: Ln = Y; 2b: Ln = Lu). The di-ligand chelated yttriurn complex 3 without alkyl moiety was isolated when the molar ratio of HL 2 to Y(CH,SiMe3)3(THF)2 increased to 2: 1. Reaction of steric phosphino beta-ketoiminato ligand HL 3 with equimolar Ln(CH2SiMe3)3(THF)2 afforded di-ligated mono-alkyl complexes (4a: Ln = Y; 4b: Ln = Lu) without occurrence of intramolecular alkylation or formation of homoleptic product. Treatment of tetradentate methoxy-amino phenol HL 4 with Y(CH2SiMe3)3(THF)2 afforded a monomeric yttrium bis-alkyl complex of THF-free. The resultant complexes were characterized by IR, NMR spectrum and X-ray diffraction analyses.All alkyl complexes exhibited high activity toward the ring-opening polymerization Of L-lactide to give isotactic polylactide with controllable molecular weight and narrow to moderate polydispersity.

Pyrrolide-supported lanthanide alkyl complexes. Influence of ligands on molecular structure and catalytic activity toward isoprene polymerization

The N,N- bidentate ligands 2- {( N- 2,6- R) iminomethyl)} pyrrole ( HL1, R) dimethylphenyl; HL2, R) diisopropylphenyl) have been prepared. HL1 reacted readily with 1 equiv of lanthanide tris( alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), affording lanthanide bis(alkyl) complexes L(1)Ln(CH2SiMe3)(2)(THF)(n) (1a, Ln= Lu, n = 2; 1b, Ln = Sc, n = 1) via alkane elimination. Reaction of the bulky ligand HL2 with 1 equiv of Ln(CH2SiMe3)(3)( THF)(2) gave the bis(pyrrolylaldiminato) lanthanide mono(alkyl) complexes L(2)(2)Ln- (CH2SiMe3)(THF) (2a, Ln) Lu; 2b, Ln = Sc), selectively. The N,N- bidentate ligand HL3, 2- dimethylaminomethylpyrrole, reacted with Ln( CH2SiMe3) 3( THF) 2, generating bimetallic bis( alkyl) complexes of central symmetry ( 3a, Ln = Y; 3b, Ln = Lu; 3c, Ln = Sc). Treatment of the N,N,N,N- tetradentate ligand H2L4, 2,2'-bis(2,2-dimethylpropyldiimino) methylpyrrole, with equimolar Lu(CH2SiMe3)(3)(THF)(2) afforded a C-2- symmetric binuclear complex ( 4). Complexes 3a, 3b, 3c, and 4 represent rare examples of THF- free binuclear lanthanide bis( alkyl) complexes supported by non- cyclopentadienyl ligands. All complexes have been tested as initiators for the polymerization of isoprene in the presence of AlEt3 and [ Ph3C][B(C6F5)(4)]. Complexes 1a, 1b, and 3a show activity, and 1b is the most active initiator, whereas 2a, 2b, 3b, 3c, and 4 are inert.

Rare earth metal bis(alkyl) complexes bearing amino phosphine ligands: Synthesis and catalytic activity toward ethylene polymerization

Reactions of neutral amino phosphine compounds HL1-3 with rare earth metal tris(alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), afforded a new family of organolanthanide complexes, the molecular structures of which are strongly dependent on the ligand framework. Alkane elimination reactions between 2-(CH3NH)-C6H4P(Ph)(2) (HL1) and Lu(CH2SiMe3)(3)(THF)(2) at room temperature for 3 h generated mono(alkyl) complex (L-1)(2)Lu(CH2SiMe3)(THF) (1). Similarly, treatment of 2-(C6H5CH2NH)-C6H4P(Ph)(2) (HL2) with Lu(CH2SiMe3)(3)(THF)(2) afforded (L-2)(2)Lu(CH2SiMe3)(THF) (2), selectively, which gradually deproportionated to a homoleptic complex (L-2)(3)Lu (3) at room temperature within a week. Strikingly, under the same condition, 2-(2,6-Me2C6H3NH)-C6H4P(Ph)(2) (HL3) swiftly reacted with Ln(CH2SiMe3)(3)(THF)(2) at room temperature for 3 h to yield the corresponding lanthanide bis(alkyl) complexes L(3)Ln(CH2SiMC3)(2)(THF)(n) (4a: Ln = Y, n = 2; 4b: Ln = Sc, n = 1; 4c: Ln = Lu, n = 1; 4d: Ln = Yb, n = 1; 4e: Ln = Tm, n = 1) in high yields. All complexes have been well defined and the molecular structures of complexes 1, 2, 3 and 4b-e were confirmed by X-ray diffraction analysis. The scandium bis(alkyl) complex activated by AlEt3 and [Ph3C][B(C6F5)(4)], was able to catalyze the polymerization of ethylene to afford linear polyethylene.

Structural diversity of lanthanide-amino acid complexes under near physiological pH conditions and their recognition of single-stranded DNA

We reported here four structures of lanthanide-amino acid complexes obtained under near physiological pH conditions and their individual formula can be described as [Tb-2(DL-Cys)(4)(H2O)(8)]Cl-2 (1), [Eu-4(mu(3)-OH)(4)(L-Asp)(2)(L-HAsp)(3)(H2O)(7)] Cl center dot 11.5H(2)O (2), [Eu-8-(L-HVal) (16)(H2O)(32)]Cl-24 center dot 12.5H(2)O (3), and [Tb-2(DL-HVal)(4)(H2O)(8)]Cl-6 center dot 2H(2)O (4). These complexes showed diverse structures and have shown potential application in DNA detection. We studied the interactions of the complexes with five single-stranded DNA and found different fluorescence enhancement, binding affinity and binding stoichiometry when the complexes are bound to DNA.

Application of room temperature ionic liquid-based extraction for metal ions

As a kind of novel green solvent, Room Temperature Ionic Liquids (RTILs) have been paid ever-increasing attentions in RTIL-based extraction for metal separation, since they have many unique proper-ties, such as non-volatile and non-flammable. The progress of that is mainly composed of the partition properties, mechanisms, defects, overcome methods and forecasts of the processes on the environmental analytical chemistry, has been reviewed.

Effects of bridge ions, DNA species, and developing temperature on flat-lying DNA monolayers

Recently, we have successfully constructed flat-lying DNA monolayers on a mica surface (J. Phys. Chem. B 2006, 110, 10792-10798). In this work, the effects of various factors including bridge ions, DNA species, and developing temperature on the configuration of DNA monolayers have been investigated by atomic force microscopy (AFM) in detail. AFM results show that the species of bridge ions and developing temperature play a crucial role during the formation process. For example, the divalent cation Zn2+ resulted in many DNA chains stuck side by side in the monolayers due to the strong interactions between it and DNA's bases or the mica surface. Most DNA chain's conglutinations disappeared when the developing temperature was higher than 40 degrees C. Cd2+ and Ca2+ produced more compact DNA monolayers with some obvious aggregations, especially for the DNA monolayers constructed by using Ca2+ as the bridge ion. Co2+ produced well-ordered, flat-lying DNA monolayers similar to that of Mg2+. Furthermore, it was found that the flat-lying DNA monolayers could still form on a mica surface when plasmid DNA pBR 322 and linear DNA pBR 322/Pst I were used as the DNA source. Whereas, it was hard to form DNA monolayers on a (3-aminopropyl)triethoxysilane-mica surface because the strong interactions between DNA and substrate prevented the lateral movement of DNA molecules.