Novel Near-Infrared Luminescent Hybrid Materials Covalently Linking with Lanthanide [Nd(III), Er(III), Yb(III), and Sm(III)] Complexes via a Primary beta-Diketone Ligand: Synthesis and Photophysical Studies

A series of novel, colorless, and transparent sot-gel derived hybrid materials Ln-DBM-Si covalently grafted with Ln(DBM-OH)(3)center dot 2H(2)O (where DBM-OH = o-hydroxydibenzoylmethane, Ln = Nd, Er, Yb, and Sin) were prepared through the primary beta-diketone ligand DBM-OH. The structures and optical properties of Ln-DBM-Si were studied in detail. The investigation results revealed that the lanthanide complexes were successfully in situ grafted into the corresponding hybrids Ln-DBM-Si. Upon excitation at the maximum absorption of ligands, the resultant materials displayed excellent near-infrared luminescence.

Novel vanadium(III) complexes with bidentate N,N-chelating iminopyrrolide ligands: synthesis, characterization and catalytic behaviour of ethylene polymerization and copolymerization with 10-undecen-1-ol

A series of novel vanadium(III) complexes bearing iminopyrrolide chelating ligands [2-(RN=CH)C4H3N]V(THF)(2)Cl-2 (2a: R = cyclohexyl; 2b: R = Ph; 2c: R = 2,6-iPr(2)C(6)H(3); 2d: R = p-CF3C6H4; 2e: R = C6F5) have been synthesized and characterized. Single-crystal X-ray diffraction revealed that complexes 2a, 2c and 2e adopt an octahedral geometry around the vanadium center. In the presence of Et2AlCl as a co-catalyst, these complexes displayed high catalytic activities up to 48.6 kg PE mmol(V)(-1) h(-1) bar(-1) for ethylene polymerization, and produced high molecular weight polymers. 2a-e/Et2AlCl catalytic systems were tolerant to elevated temperature (70 degrees C) and yielded unimodal polyethylenes, indicating the single site behaviour of these catalysts. By pre-treating with equimolar amounts of alkylaluminums, functional alpha-olefin 10-undecen-1-ol can be efficiently incorporated into polyethylene chains. 10-Undecen-1-ol incorporation can easily reach 15.8 mol% under the mild conditions.

Separation of scandium(III) from lanthanides(III) with room temperature ionic liquid based extraction containing Cyanex 925

The separation of Sc(III) from Y(III), La(III) and Yb(III) in [C(8)mim][PF6] containing Cyanex 925 has been investigated, and is reported in this paper. A cation exchange mechanism of Sc(III) in [C(8)mim][PF6] and Cyanex 925 is proposed by study of the influence of anionic and cationic species on the extraction. The coefficient of the equilibrium equation of Sc(III) was confirmed by slope analysis of log D-Sc vs log [Cyanex 925], and the loading capacity also confirmed the stoichiometry of Cyanex 925 to Sc(III) was close to 3:1. Infrared data for Cyanex 925 saturated with Sc(III) in [C(8)mim][PF6] indicated strong interaction between P=O of Cyanex 925 and Sc(III). In addition, the relationship between log D-Sc and temperature showed that temperature had little influence on the extraction process, and the resulting thermodynamic parameters indicated that an exothermic process was involved.

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.

Supramolecular architectures, photophysics, and electroluminescence of 1,3,4-oxadiazole-based iridium(III) complexes: From mu-dichloro bridged dimer to mononuclear complexes

One mu-dichloro bridged diiridium complex and three mononuclear iridium(III) complexes based on the 1,3,4-oxadiazole derivatives as cyclometalated ligands and acetylacetonate (acac) or dithiolates O,O'-diethyldithiophosphate (Et(2)dtp) or N,N'-diethyldithiocarbamate (Et(2)dtc) as ancillary ligands have been synthesized and systematically studied by X-ray diffraction analysis. The results reveal that three mononuclear complexes all adopt distorted octahedral coordination geometry around the iridium center by two chelating ligands with cis-C-C and trans-N-N dispositions, which have the same coordination mode as the diiridium dimer. The dinuclear complex crystallizes in the monoclinic system and space group C2/c, whereas three mononuclear iridium complexes are all triclinic system and space group P(1) over bar. In the stacking structure of the dimer, one-dimensional tape-like chains along the b-axis are formed by hydrogen bondings, which are strengthened by pi stacking interactions between phenyl rings of 1,3,4-oxadiazole ligands. Then these chains assemble a three-dimensional alternating peak and valley fused wave-shape structure. In each stacking structure of three mononuclear complexes, two molecules form a dimer by the C-H center dot center dot center dot O hydrogen bondings, and these dimers are connected by pi stacking interactions along the b-axis, constructing a zigzag chain.

Synthesis, structure and luminescence properties of zinc (II) complexes with terpyridine derivatives as ligands

Five zinc (II) complexes (1-5) with 4 '-phenyl-2,2 ':6 ',2 ''-terpyridine (ptpy) derivatives as ligands have been synthesized and fully characterized. The para-position of phenyl in ptpy is substituted by the group (R), i.e. tert-butyl (t-Bu), hexyloxy (OHex), carbazole-9-yl (Cz), naphthalen-1-yl-phenyl-amine-N-yl (NPA) and diphenyl amine-N-yl (DPA), with different electron-donating ability. With increasing donor ability of the R, the emission color of the complexes in film was modulated from violet (392 nm) to reddish orange (604 nm). The photoexcited luminescence exhibits significant solvatochromism because the emission of the complexes involves the intra-ligand charge transfer (ILCT) excited state. The electrochemical investigations show that the complexes with stronger electro-donating substituent have lower oxidation potential and then higher HOMO level. The electroluminescence (EL) properties of these zinc (II) complexes were studied with the device structure of ITO/PEDOT/Zn (II) complex: PBD:PMMA/BCP/AlQ/ LiF/Al. Complexes 3, 4 and 5 exhibit EL wavelength at 552, 600 and 609 nm with maximum current efficiency of 5.28, 2.83 and 2.00 cd/A, respectively.

Investigation of sandwiched gadolinium(III) complexes with tungstosilicates as potential MRI contrast agents

Two gadolinium-sandwiched complexes with tungstosilicates, K-13[Gd(SiW11O39)(2)] (Gd(SiW11)(2)) and K11H6[Gd2O3(SiW9O34)(2)] (Gd-3(SiW9)(2)), have been investigated by in vitro and in vivo experiments as potential contrast agents for magnetic resonance imaging (MRI). T-1-relaxivity of Gd(SiW11)(2)was 6.59 mM(-1) . s(-1) in aqueous solution and 6.85 mM(-1) . s(-1) in 0.725 mmol . L-1 bovine serum albumin solution at 25degreesC and 9.39 T, respectively. The corresponding T-1-relaxivity of Gd-3(SiW9)(2) was 12.6 and 19.3 mM(-1) . s(-1) per Gd, respectively. MRI for Sprague-Dawley rats showed longer and more remarkable enhancement in rat liver after i.v. injection of these two complexes: 39.4 +/- 3.9% and 57.4 +/- 11.6% within the first 30 min after injection, 31.2 +/- 2.6% and 39.9 +/- 7.6% in the next 60 min for Gd(SiW11)(2) and Gd-3(SiW9)(2) at doses of 0.081 and 0.084 mmol Gd/kg, respectively. Our preliminary in vitro and in vivo study indicates that Gd(SiW11)(2) and Gd-3(SiW9)(2) are favorable candidates for hepatic contrast agents for MRI. However, the two complexes exhibit higher acute toxicity and need to be modified and studied further before clinical use.

Tuning the saturated red emission: synthesis, electrochemistry and photophysics of 2-arylquinoline based iridium(III) complexes and their application in OLEDs

A series of novel iridium(III) complexes with two 2-arylquinoline derivatives as cyclometalated ligands and one monoanionic ligand, such as acetylacetonate (acac), N,N'-diethyldithiocarbamate (Et(2)dtc) and O,O'-diethyldithiophosphate (Et(2)dtp), as ancillary ligands have been synthesized and structurally characterized by H-1 NMR, MS and elemental analysis (EA). The cyclic voltammetry, absorption, emission and electroluminescence properties of these complexes were systematically investigated. Through extending pi-conjugation, introducing electron-donating groups in the ligand frame, or changing the ancillary ligands, the HOMO energy levels of the iridium(III) complexes can be tuned, while their LUMO levels remain little affected; in consequence, the emission wavelengths of the iridium(III) complexes can be tuned in the range 606-653 nm. The highly efficient organic light-emitting diodes (OLEDs) with saturated red emission have been demonstrated. A maximum current efficiency of 10.79 cd A(-1), at a current density of 0.74 mA cm(-2), with an emission wavelength of 616 nm and Commisioon Internationale de L'Eclairage (CIE) coordinates of (0.65, 0.35), which are very close to the National Television System Comittee (NSTC) standard red emission, have been achieved when using complex (DPQ)(2)Ir(acac) as a phosphor dopant.

Syntheses, structures and near-IR luminescent studies on ternary lanthanide (Er-III, Ho-III, Yb-III, Nd-III) complexes containing 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate

The ligand Hhfth [4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dione], which contains a heptafluoropropyl group, has been used to synthesize several new ternary lanthanide complexes (Ln = Er, Ho, Yb, Nd) in which the synergistic ligand is 1,10-phenanthroline (phen) or 2,2'-bipyridine (bipy). The two series of complexes are [Ln(hfth)(3)phen] [abbreviated as (Ln)1, where Ln = Er, Ho, Yb] and [Ln(hfth)(3)bipy] [abbreviated as (Ln)2, where Ln = Er, Ho, Yb, Nd]. Members of the two series have been structurally characterized. The growth morphology, diffuse reflectance (DR) spectra, thermogravimetric analyses, and photophysical studies of these complexes are described in detail. After ligand-mediated excitation of the complexes, they all show the characteristic near-infrared (NIR) luminescence of the corresponding Ln(3+) ions (Ln = Er, Ho, Yb, Nd). This is attributed to efficient energy transfer from the ligands to the central Ln(3+) ions, i.e. an antenna effect. The heptafluorinated substituent in the main hfth sensitizer serves to reduce the degree of vibrational quenching. With these NIR-luminescent lanthanide complexes, the luminescent spectral region from 1300 to 1600 nm, which is of particular interest for telecommunication applications, can be covered completely.

Synthesis, structure, electrochemistry, photophysics and electroluminescence of 1,3,4-oxadiazole-based ortho-metalated iridium(III) complexes

Four new iridium(III) complexes 1-4, with 1,3,4-oxadiazole derivative as cyclometalated ligand for the first time, have been synthesized and structurally characterized by NMR, EA, MS and X-ray diffraction analysis (except 1). The stronger ligand field strength of the dithiolate ancillary ligands results in higher oxidation potentials and lower HOMO energy levels of complexes than acetylacetone. The absorption spectra of these complexes display low-energy metal-to-ligand charge transfer transition ranging from 350 to 500 nm. Complexes with dithiolate ancillary ligand emit at maximum wavelengths of ca. 500 nm, blue shifting 17 and 11 nm with respect to their counterpart with acetylacetone ligand. The electrophosphorescent devices with 2-4 as phosphorescent dopant in emitting layer have been fabricated. All devices have a low turn-on voltage in the range of 4.5 and 4.9 V. A high-efficiency green emission with maximum luminous efficiency of 5.28 cd/A at current density of 1.37 mA/cm(2) and a maximum brightness of 2592 cd/m(2) at 15.2 V has been achieved in device using 2 as emitter.

Highly efficient iridium(III) complexes with diphenylquinoline ligands for organic light-emitting diodes: Synthesis and effect of fluorinated substitutes on electrochemistry, photophysics and electroluminescence

A series of novel cyclometalated iridium(III) complexes bearing 2,4-diphenylquinoline ligands with fluorinated substituent were prepared and characterized by elemental analysis, NMR and mass spectroscopy. The cyclic voltammetry, absorption, emission and electroluminescent properties of these complexes were systematically investigated. Electrochemical studies showed that the oxidation of the fluorinated complexes occurred at more positive potentials (in the range 0.57-0.69 V) than the unfluorinated complex 1 (0.42 V). In view of the energy level, the lowering of the LUMO by fluorination is significantly less than that of the HOMO. The weak and low energies absorption bands in the range of 300-600 nm are well resolved, likely associated with MLCT and (3)pi-pi* transitions. These complexes show strong orange red emission both in the solution and solid state. The emission maxima of the fluorinated complexes showed blue shift by 9, 24 and 15 nm for 2, 3 and 4, respectively, with respect to the unfluorinated analogous 1. Multilayered organic light-emitting diodes (OLEDs) were fabricated by using the complexes as dopant materials. Significantly higher performance and lower turn-on voltage were achieved using the fluorinated complexes as the emitter than that using the unfluorinated counterpart 1 under the same doping level.

Tuning of emission: Synthesis, structure and photophysical properties of imidazole, oxazole and thiazole-based iridium (III) complexes

Three new iridium (III) complexes with two cyclometalated (CN)-N-boolean AND ligands (imidazole, oxazole and thiazole-based, respectively) and one acetylacetone (acac) ancillary ligand have been synthesized and fully characterized. The structure of the thiazole-based complex has been determined by single crystal X-ray diffraction analysis. The Ir center was located in a distorted octahedral environment by three chelating ligands with the N-N in the trans and C-C in the cis configuration. By changing the hetero-atom of (CN)-N-boolean AND ligands the order S, O and N, a marked and systematic hypsochromic shift of the maximum emission peak of the complexes was realized. The imidazole-based complex emits at a wavelength of 500 nm, which is in the blue to green region. The tuning of emission wavelengths is consistent with the variation of the energy gap estimated front electrochemistry results. An electroluminescent device using the thiazole-based complex as a dopant in the emitting layer has been fabricated. A highly efficient yellow emission with a maximum luminous efficiency of 9.8 cd/A at a current density of 24.2 mA/cm(2) and a maximum brightness of 7985 cd/m(2) at 19.6 V has been achieved.

Syntheses, structures and luminescence of silver(I) sulfonate complexes with PPh3 ligand

In this paper, four new luminescent silver(I) sulfonate complexes with PPh3, namely Ag(L1)(PPh3)(2) (1), Ag(L2)(PPh3)(3) (2), [Ag-2(L3)(PPh3)(4) (H2O)center dot 1.5CH(3)CN center dot 0.5H(2)O (3) and [Ag-4(L4)(PPh3)(10)]center dot 8H(2)O (4), where L1=p-toluenesulfonate, L2=1-naphthalenesulfonate, L3=3-carboxylate-4-hydroxybenzenesulfonate, L4=1, 3, 6, 8-pyrenetetrasulfonatc and PPh3=triphenylphosphine, have been synthesized and characterized. The crystal structures were determined by single-crystal X-ray diffraction method. Compounds 1, 2, 3 and 4 adopt discrete structures rather than polymeric structures. Compounds I and 2 show mononuclear structures while 3 and 4 are dinuclear and tetranuclear molecules, respectively. Moreover the numbers of PPh3 molecules coordinating to one silver center are two or three. The photoluminescent properties of 1, 2 and 3 are discussed.

Synthesis and characterization of novel orange-emitting iridium(III) complexes with diphenylquinoline ligands containing fluorinated substituent

Three new cyclometalated iridium(III) complexes based on ligands of diphenylquinoline with fluorinated substituents were prepared, and characterized by elemental analysis (EA), H-1 NMR, and mass spectroscopy (MS). The photophysical and electrophosphorescent properties of the complexes were briefly discussed.

The structural transition of DNA-Tris(1,10-phenanthroline) cobalt(III) complexes in ethanol-water solution

The interaction of DNA with Tris(1,10-phenanthroline) cobalt(III) was studied by means of atomic force microscopy. Changes in the morphologies of DNA complex in the presence of ethanol may well indicate the crucial role of electrostatic force in causing DNA condensation. With the increase of the concentration of ethanol, electrostatic interaction is enhanced corresponding to a lower dielectric constant. Counterions condense along the sugar phosphate backbone of DNA when e is lowered and the phosphate charge density can thus be neutralized to the level of DNA condensation. Electroanalytical measurement of DNA condensed with Co(phen)(3)(3+) in ethanol solution indicated that intercalating reaction remains existing. According to both the microscopic and spectroscopic results, it can be found that no secondary structure transition occurs upon DNA condensing. B-A conformation transition takes place at more than 60% ethanol solution.