Near-infrared luminescent mesoporous MCM-41 materials covalently bonded with ternary thulium complexes

Two beta-diketones 4,4,4-trifluoro-1-2-thenoyl-1,3-butanedione (Htta) and 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione (Htfnb), which contain trifluoroalkyl chain, were selected as the main sensitizer for synthesizing Tm(L)(3)phen (L = tta, tfnb) complexes. The two near-infrared (NIR) luminescent thulium complexes have been covalently bonded to the ordered mesoporous material MCM-41 via a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) [The resultant mesoporous materials are denoted as Tm(L)(3)phen-MCM-41 (L = tta, tfnb)]. The Tm(L)(3)phen-MCM-41 (L = tta, tfnb) mesoporous materials were characterized by small-angle Xray diffraction (XRD) and N-2 adsorption/desorption, and they show characteristic mesoporous structure of MCM-41.

Syntheses, crystal structures, visible and near-IR luminescent properties of ternary lanthanide (Dy3+, Tm3+) complexes containing 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 1,10-phenanthroline

The ligands 4,4,4-trifluoro-1-phenyl-1.3-butanedione (Hbfa) and 1,10-phenanthroline (phen) were used to prepare ternary lanthanide (Ln) complexes [Dy(bfa)(3)phen and Tm(bfa)(3)phen]. Crystal data: Dy(bfa)(3)phen C(42)H(26)FqN(2)O(6)Dy, triclinic, P (1) over bar, a= 9.9450(6) angstrom, b = 14.0944(9) angstrom, c = 14.6043(9) angstrom, alpha = 82.104(1)degrees, beta = 87.006(1)degrees, gamma = 76.490(1)degrees, V = 1971.1(2)angstrom(3), Z = 2; Tm(bfa)(3)phen C42H26F9N2O6Tm, triclinic, P (1) over bar, a = 9.898(5)angstrom, b = 13.918(5)angstrom, c = 14.753(5)angstrom, a = 83.517(5)degrees, alpha = 86.899(5)degrees, gamma = 76.818(5)degrees, V = 1965.3(14)angstrom(3), Z = 2. The coordination number of the central Ln(3+) (Ln = Dy, Tm) ion is eight, with six oxygen atoms from three Hbfa ligands and two nitrogen atoms from the phen ligand.

Near-infrared luminescence from sol-gel materials doped with holmium(III) and thulium(III) complexes

A series of ternary Ln(tta)(3)L complexes (Ln = Ho, Tm; Htta = 2-thenoyltrifluoroacetone; L = 1,10-phenanthroline, 2,2'-bipyridine, or triphenyl phosphate oxide) and their corresponding sol-gel hybrid materials formed via the in situ synthesis process (designated as Ln-T-L gel) were reported. The complexes and the gels were studied in detail, which suggest the complexes have been successfully synthesized in the corresponding gels.

Synthesis, characterization, and near-infrared luminescent properties of the ternary thulium complex covalently bonded to mesoporous MCM-41

The crystal structure of a ternary Tm(DBM)(3)phen complex (DBM - dibenzoylmethane; phen = 1. 10-phenanthroline) and the synthesis of hybrid mesoporous material in which the complex covalently bonded to mesoporous MCM-41 are reported. Crystal data: Tm(DBM)(3)phen C59H47N2O7Tm, monoclinic P21/c, a = 19.3216(12) A, b = 10.6691(7) A, c = 23.0165(15)A, alpha = 90, beta = 91.6330(10), gamma = 90, V = 4742.8(5) A(3), Z = 4. The properties of the Tm(DBM)(3)phen complex and the corresponding hybrid mesoporous material [Tm(DBM)(3)phen-MCM-41] have been studied. The results reveal that the Tm(DBM)(3)phen complex is successfully covalently bonded to MCM-41.

Forced Dissociation of Selectin-ligand Complexes Using Steered Molecular Dynamics Simulation

Selectin-ligand interactions are crucial to such biological processes as inflammatory cascade or tumor metastasis. How transient formation and dissociation of selectin-ligand bonds in blood flow are coupled to molecular conformation at atomic level, however, has not been well understood. In this study, steered molecular dynamics (SMD) simulations were used to elucidate the intramolecular and intermolecular conformational evolutions involved in forced dissociation of three selectin-ligand systems: the construct consisting of P-selectin lectin (Lec) and epidermal growth factor (EGF)-like domains (P-LE) interacting with synthesized sulfoglycopeptide or SGP-3, P-LE with sialyl Lewis X (sLeX), and E-LE with sLeX. SMD simulations were based on newly built-up force field parameters including carbohydrate units and sulfated tyrosine(s) using an analogy approach. The simulations demonstrated that the complex dissociation was coupled to the molecular extension. While the intramolecular unraveling in P-LESGP-3 system mainly resulted from the destroy of the two anti-parallel sheets of EGF domain and the breakage of hydrogen-bond cluster at the Lec-EGF interface, the intermolecular dissociation was mainly determined by separation of fucose (FUC) from Ca2+ ion in all three systems. Conformational changes during forced dissociations depended on pulling velocities and forces, as well as on how the force was applied. This work provides an insight into better understanding of conformational changes and adhesive functionality of selectin-ligand interactions under external forces.

Synthesis of nickel(II) complexes of alpha-isoxazolylazo-beta-diketones and their absorption of spin-coating films and thermal properties for HD-DVD-R

Three kinds of new nickel(II) complexes of alpha-isoxazolylazo-beta-diketones with blue-violet light absorption were synthesized. Their structures were postulated based on elemental analysis, MS and FT-IR spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. The absorption properties and thermal stability of these complexes were discussed. The static optical recording test for high density digital versatile disc-recordable (HD-DVD-R) system was also studied. (c) 2005 Elsevier B.V. All rights reserved.

Rare earth doped beta-diketone complexes as promising high-density optical recording materials for blue optoelectronics

Some kinds of rare earth beta-diketone complexes with blue-violet light absorption edge were synthesized using the ligands of thenoyltrifluoroacctone (HTTA), 2, 2'-dipyridyl (BIPY) and different metal ions (Gd3+, Sm3+ and La3+). Their contents, structures and optoelectronic parameters were monitored by elemental analysis, MS, IR and UV spectra. The solubility of rare earth beta-diketone complexes in 2, 2, 3, 3-tetrafluoro-1-propanol (TFP) and absorption properties of their films in the region 300-800 nm were measured. The influence on the difference of absorption maximum from rare earth beta-diketone complexes to beta-diketone ligand by different metal ions was studied. In addition, the thermal stability of rare earth beta-diketone complexes was also reported. (C) 2005 Elsevier B.V. All rights reserved.

Spectroscopic and thermal properties of short wavelength metal (II) complexes containing alpha-isoxazolylazo-beta-diketones as co-ligands

Two new azo dyes of alpha-isoxazolylazo-beta-dilcetones and their Ni(II) and Cu(II) complexes with blue-violet light wavelength were synthesized using a coupling component, different diazo components and metal (II) ions (Ni2+ and Cu2+). Based on the elemental analysis, MS spectra and FT-IR spectral analyses, azo dyes were unequivocally shown to exist as hydrazoketo and azoenol forms which were respectively obtained from the solution forms and from the solid forms. The action of sodium methoxide (NaOMe) on azo dyes in solutions converts hydrazoketo form into azoenol form, so azo dyes are coordinated with metal (II) ions as co-ligands in the azoenol forms. The solubility of all the compounds in common organic solvents such as 2,2,3,3-tetrafluoro-1-propanol (TFP) or chloroform (CHCl3) and absorption properties of spin-coating thin films were measured. The difference of absorption maxima from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. It is found that these new metal (II) complexes had potential application for high-density digital versatile disc-recordable (HD-DVD-R) system due to their good solubility in organic solvents, reasonable and controllable absorption spectra in blue-violet light region and high thermal stability. (c) 2004 Elsevier B.V. All rights reserved.

Optical parameters and absorption of copper (II)-azo complexes thin films as optical recording media

Smooth thin films of three kinds of azo dyes of 2-(5'-tert-butyl-3'-azoxylisoxazole)-1, 3-diketones and their copper (II)-azo complexes were prepared by the spin-coating method. Absorption spectra of the thin films on a glass substrate in the 300-600 nm wavelength region were measured. Optical constants (complex refractive index N=n+ik) and thickness of the thin films prepared on single-crystal silicon substrate in the 300-600 nm wavelength region were investigated on rotating analyzer-polarizer type of scanning ellipsometer, and dielectric constants epsilon(epsilon=epsilon(1)+i epsilon(2)), absorption coefficients alpha as well as reflectance R of thin films were then calculated. In addition, one of the copper (II)-azo complex thin film prepared on glass substrate with an Ag reflective layer was also studied by atomic force microscopy (AFM) and static optical recording. AFM study shows that the copper (II)-azo complex thin film is very smooth and has a root mean square surface roughness of 1.89 nm. Static optical recording shows that the recording marks on the copper (II)-azo complex thin film are very clear and circular, and the size of the minimal recording marks can reach 200 nm. (c) 2004 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic and thermal properties of nickel (II)-azo complexes with blue-violet light wavelength

A novel azo dye containing isoxazole ring and beta-diketone derivative (TIAD) and its two nickel (II) complexes (Ni (II)-ETIAD and Ni (II)-HTIAD) were synthesized in order to obtain a blue-violet light absorption and better thermal stability as a promising organic storage material for next generation of high density digital versatile disc-recordable (HD-DVD-R) systems that uses a high numerical aperture of 0.85 at 405 nm wavelength. Their structures were confirmed on the basis of elemental analysis, MS, FT-IR, UV-Vis and magnetic data. Their solubility in 2,2,3,3-tetrafluoro-1-propanol (TFP) and absorption properties of thin film were measured. The difference of absorption maximum from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. (C) 2004 Elsevier Ltd. All rights reserved.

Synthesis, spectroscopic properties and thermal stability of metal(II) tetraazaporphyrin complexes with two strong wavelength absorption

Three kinds of metal(II) tetraazaporphyrin complexes with blue-violet and red light wavelength absorption were synthesized by refluxing tetraazaporphyrin ligand and different metal(II) ions, respectively. Their structures were confirmed by elemental analysis, LDI-TOF-MS, FT-IR and UV-Vis. The solubility of metal(II) tetraazaporphyrin complexes in organic solvents and absorption properties of their chloroform solution and films on K9 glass in the region 250-800 nm were measured. The influence on the difference of absorption maximum from metal(II) tetraazaporphyrin complexes to tetraazaporphyrin ligand by different metal(II) ions was studied. In addition, the thermal stability of the complexes was also evaluated. (c) 2006 Elsevier Ltd. All rights reserved.

Determination and analysis of the optical constants of thin films of nickel(II) and copper(II) hydrazone complexes by spectroscopic ellipsometry

Thin films of four nickel(II) and copper(II) hydrazone complexes, which will hopefully be used as recording layers for the next-generation of high-density recordable disks, were prepared by using the spin-coating method. Absorption spectra of the thin films on K9 optical glass substrates in the 300-700 nm wavelength region were measured. Optical constants (complex refractive indices N) and thickness d of the thin films prepared on single-crystal silicon substrates in the 275-675 nm wavelength region were investigated on a rotating analyzer-polarizer scanning ellipsometer by fitting the measured ellipsometric angles (Psi(lambda) and Delta(lambda)) with a 3-layer model (Si/dye film/air). The dielectric functions epsilon and absorption coefficients alpha as a function of the wavelength were then calculated. Additionally, a design to achieve high reflectivity and optimum dye film thickness with an appropriate reflective layer was performed with the Film Wizard software using a multilayered model (PC substrate/reflective layer/dye film/air) at 405 nm wavelength.

Optical properties of nickel(II)-azo complexes thin films for potential application as high-density recordable optical recording media

Smooth thin films of three kinds of nickel(II)-azo complexes were prepared by the spin-coating method. Absorption spectra of the thin films on K9 glass substrate in the 300-600 nn wavelength region were measured. Optical constants (complex refractive index N = n + ik) and thickness of the thin films prepared on single-crystal silicon substrate in the 300-600 nm wavelength region were investigated on rotating analyzer-polarizer type of scanning ellipsometer, and dielectric constants epsilon (epsilon = epsilon(1) + i epsilon(2)), absorption coefficients a as well as reflectance R of thin films were then calculated at 405 nm. In addition, in order to examine the possible use of nickel(II)-azo complex thin film as an optical recording medium, one of the nickel(II)-azo complex thin film prepared on K9 glass substrate with an Ag reflective layer was also studied by atomic force microscopy and static optical recording. The results show that the nickel(II)-azo complex thin film is smooth and has a root mean square surface roughness of 2.25 nm, and the recording marks on the nickel(II)-azo complex thin film are very clear and circular, and their size can reach 200 nn or less. (c) 2006 Elsevier Ltd. All rights reserved.

Synthesis, spectral, and thermal characterizations of Ni(II) and Cu(II) beta-diketone complexes with thenoyltrifluoroacetone ligand

Two kinds of nickel(II) and copper(II) P-diketone complexes derived from thenoyltrifluoroacetone ligand with blue-violet light absorption were synthesized by reacting free ligand and different metal(II) ions in sodium methoxide solution. Their structures were postulated based on elemental analysis, ESI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. Their solubility in organic solvents, absorption properties of thin film and thermal stability of these complexes were evaluated. (c) 2006 Elsevier B.V. All rights reserved.

Spectroscopic, and thermal studies of some new binuclear transition metal(II) complexes with hydrazone ligands containing acetoacetanilide and isoxazole

A new chelating ligand, 2-(2-(5-tert-butylisoxazol-3-yl)hydrazono)-N-(2,4-dimethylphenyl)-3-oxobutanamide (HL), and its four binuclear transition metal complexes, M-2(L)(2) (mu-OCH3)(2) [M = Ni(II), Co(II), Cu(II), Zn(II)], were synthesized using the procedure of diazotization, coupling and metallization. Their structures were postulated based on elemental analysis, H-1 NMR, MALDI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films of these complexes on K9 glass substrates were prepared using the spin-coating method and their absorption properties were evaluated. The thermal properties of the metal(II) complexes were investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC. Different thermodynamic and kinetic parameters namely activation energy (E