Synthesis,Crystal Structure,Spectroscopic Property and Redox Behavior of Zinc(Ⅱ) Complexes Containing Oligoaniline-functionalized Terpyridine Ligands

Two novel mono-nuclear zinc（Ⅱ） complexes with oligoaniline-functionalized terpyridine ligands have been synthesized and verified by 1H-NMR,13C-NMR,Elemental Analysis （EA） and X-ray Diffraction （XRD）. The UV-vis spectra show the ligand-centered （LC） π-π＊ transitions and intra-ligand charge transfer （1ILCT） transitions,and the 1ILCT band red-shifts with the increasing number of aromatic amine groups in the ligands. Complex [Zn（L1）2]（PF6）2 with an aromatic amine group in ligand shows a strong emission peak at 523 nm in the MeCN solution at 293 K and a blue-shifted band at 517 nm in the alcoholic glass at 77 K. However,for complex [Zn（L2）2]（PF6）2 containing aniline dimer modified ligand,no apparent emission can be observed in the MeCN solution at room temperature due to a PET non-radiative decay pathway. Both of them show multiplicate redox processes based on oligoaniline and terpyridine units. The shifts of redox potentials also reflect the D-A interactions between the oligoaniline units and [Zn（TPY）2]2＋ core.

Transient Spectroscopic Properties of [60]Fullerene-Containing Cyclic Sulphoxide

The properties of the triplet excited state of [60]fullerene-containing cyclic sulphoxide have been investigated by time-resolved absorption spectroscopy. Transient absorption bands of [60]fullerene-containing cyclic sulphoxide showed two decay-components, which were attributed to triplet excited states of different spin multiplicity. The properties of photoexcited states of [60]fullerene-containing cyclic sulphoxide are also reported.

Spectroscopic Properties of Ce:YAP Scintillation Crystal Grown by Temperature Gradient Technique

Spectroscopic properties of Ce-doped yttrium orthoaluminate （Ce：YA1O3 or Ce：YAP） crystals gown by temperature gradient technique （TGT） were investigated, and the effects of the growth conditions on the properties were analyzed. Methods of optical absorption （OA）, photoluminescence （PL）, photoluminescence decay （PLD）, X-my excited luminescence （XL） and cathodeluminescence （CL） were used in these investigations. The results showed that the absorption band peak at 202,394 and 532 nm originated from F and F^＋ color center induced by the weak reducing growth atmosphere, green emission band near 500 nm derived from Ce3^＋ -Ce^3＋ pairs and band at 650 - 850 nm from some unintentional impurity in crystals.

Raman and Infrared Spectroscopic Investigation of Some Hydrous LnTPPTS Complexes(Ln=La,Sm)

Ferrocenlyselenides(C 5H 5FeC 5H 4SeR,Fe(C 5H 4SeR) 2) and their complexes of metal Pt,Pd,Rh(R=undecenyl,benzyl,phenyl)have been prepared.The spectroscopic characterization has been examined by mass spectrum,XPS,IR and NMR.IR,NMR spectra of C 5H 5Fe C 5H 4Se(CH 2) 9 CH=CH 2PtCl 2 reveal C=C double bond in Fe(C 5H 4Se(CH 2) 9CH=CH 2) 2 Pt Cl 2 is free because of binding with Pt(Ⅱ).The results obtained from 1H, 13 C and 77 Se NMR indicate that invertomers of meso and dl species existence.The ratio of meso/dl for BUnSeF Pt is ca 70/30,whereas four and three invertomers for BUnSeF Pt and BBSeFPd have been clearly observed from 1H NMR spectra.

Preparation and Spectroscopic Properties of Pr^(3＋)-doped Transparent Glass-ceramic Containing LiYF_4 Nanocrystals

Pr^（3＋）-doped transparent oxyfluoride glass-ceramic containing tetragonal LiYF_4 nanocrystals has been synthesized by melting-quenching method and subsequent thermal treatment and spectroscopic properties of Pr^（3＋） ions were investigated. The crystalline phase and microstructure of the LiYF_4 nanocrystals were studied by X-ray diffraction（XRD） and transmission electron microscopy（TEM）, respectively. Compared with those of Pr^（3＋）-doped glass（Pr^（3＋）：PG）, the sharp absorption and emission bands of Pr^（3＋）-doped glass-ceramic（Pr^（3＋）：GC） reveal parts of Pr^（3＋） ions are incorporated into LiYF_4 nanocrystals. The peak absorption cross-section at 443 nm（~3H_4 → ~3P_2） adds to 110% and the full width at half maximum（FWHM） for the band around 443 nm reduces from 22 to 14 nm after crystallization. The fluorescence lifetime of the ~3P_0 multiplet of Pr^（3＋） ions increases from 5.35 to 11.14 μs after crystallization. The results indicate that this glass-ceramic is promising to be a visible laser material.

A Novel Palladium(Ⅱ)Complex Self-assembled from Anthracene-9-carboxylic Acid:Synthesis,Crystal Structure and Spectroscopic Properties

A novel palladium（II） complex [（TMEDA）Pd（anca）2].2DMSO （1, TMEDA = N,N,N＇,N＇-tetramethylethylethylenediamine, anca = anthracene-9-carboxylic acid） was synthesized and characterized by single-crystal X-ray diffraction, 1H NMR, UV-Vis and fluorescence spectroscopy. The cell belongs to orthorhombic Aba2 space group with a = 19.698（7）, b = 21.045（7） c = 9.062（3） A, Z = 4, V= 3757（2） A3, C40H46N206PdS2, Mr = 821.31, D, = 1.452 g/cm3, F（000） = 1704, the final R = 0.0272, wR = 0.0667 and GOOF = 0.999. Complex 1 exhibits an interesting distorted clip-shaped molecular configuration which is stabilized by intramolecular C-H...O hydrogen bonds. The cells are packed into a 3D supramolecular structure based on the intermolecular C-H...zr interactions which further construct the tubular channels serving as guest molecular channels to include the DMSO solvent molecules inside. Furthermore, the spectroscopic properties of 1 were also investigated.

Spectroscopic Properties and Judd-Ofelt Theory Analysis of Er^(3+)-Doped Heavy Metal Oxyfluoride Silicate Glass

Er^(3+)-doped heavy metal oxyfluoride silicate glass was fabricated and characterized, and the absorption spectrum and fluorescence spectrum of the glass were studied. The Judd-Ofelt intensity parameters Ω_t (t =2, 4, 6), spontaneous transition probability, fluorescence branching ratio and radiative lifetime of each energy levels for Er^(3+) were calculated by Judd-Ofelt theory, and stimulated emission cross-section of (()~4I_(13/2))→(()~4I_(15/2)) transition was calculated by McCumber theory. The results show that fluorescence full width at half maximum and stimulated emission cross-section of Er^(3+)-doped heavy metal oxyfluoride silicate glass are broad and large, respectively. Compared with other host glasses, the gain bandwidth property of Er^(3+)-doped heavy metal oxyfluoride silicate glass is close to those of tellurite and bismuth glasses, and has advantage over those of silicate, phosphate and germante glasses.

Influence of B_2O_3 on Spectroscopic Properties of Er^(3+)/Yb^(3+) Co-Doped Tungsten-Tellurite Glasses

A series of novel Er^3＋/Yb^3＋ co-doped （85- x ） TeO2-15WO3-xB2O3 （TWB;x=2%,5%,8%（mole fraction） ） glasses were prepared. Influence of B203 on the spectroscopic properties of Er^3＋/Yb^3＋ co-doped tungsten-tellurite glasses were investigated. It is found that the intensity of 1.5μm fluorescence, lifetime of the ^4I13/2 level and upconversion fluorescence all decrease with the increase of B2O3 content. The product of full width at half maximum （FWHM） and stimulated emission cross-section （σe^peak） of Er^3＋ ：^4I13/2→^4I15/2 transition has an optimum when B203 is 5% （mole fraction）. The emission spectra of Er^3＋ ： ^4I13/2→^4I15/2 transition was analyzed using peak-fit routine, and an equivalent four-level system was proposed to estimate the stark splitting for the 411512 and ^4I13/2 levels of Er^3＋ ions in TWB glasses at room temperature.

Spectroscopic properties of Er/Ce-codoped La_3Ga_5SiO_(14)

The Er-single-doped and Er/Ce-codoped La3Ga5SiO14 polycrystalline powders are synthesized by the solid-phase synthesis method. The room-temperature luminescence spectra of the samples are investigated. The Near-infrared- region spectroscopic properties of Er3＋ ions in the La3GasSiO14 systems are analysed with Judd-Ofelt theory and rate equations. The effective deactivating effect of Ce3＋ ions on Er3＋ ions is confirmed.

Growth and Spectroscopic Investigations of Disordered Nd^(3+):Li_3Ba_2La_3(MoO_4)_8 Crystal

Nd3＋： Li3Ba2La3（MoO4）8 crystal has been grown from a flux of Li2MoO4 by the top seeded solution growth method （TSSG） and its structure was confirmed by X-ray diffraction. The polarized absorption spectra, fluorescence spectra and fluorescence decay curve of the crystal were measured. The main spectral parameters were calculated by the Judd-Ofelt theory and compared with other Nd-doped crystals. The broad absorption bands and the large absorption cross sections around 805 nm indicate that the crystal is very suitable for diode-laser pumping. The broad emission bands around 1060 nm show that the crystal is a potential medium for tunable and short pulse lasers. The quantum efficiency of the crystal is up to 95%, which is higher than the value for Nd3＋：YVO4 and Nd3＋：YAG and comparable to that of other disordered molybdate crystals. The excellent spectroscopic properties show that Nd3＋：Li3Ba2La3（MoO4）8 crystal may be regarded as a potential solid state laser host material for diode laser pumping.

Growth and Spectroscopic Properties of Nd^(3+):Sr_3Gd_2(BO_3)_4 Crystal

This paper reports the growth, X-ray diffraction and spectroscopy of Nd3＋：Sr3Gd2（BO3）4 crystal. A Nd3＋：Sr3Gd2（BO3）4 crystal with dimensions of φ20 × 45 mm3 has been grown by the Czochralski method. Nd3＋：Sr3Gd2（BO3）4 crystal belongs to the orthorhombic system, space group Pnma （D2h） with a = 0.7401, b = 1.604 and c = 0.8755 nm. The absorption and emission spectra of Nd3＋：Sr3Gd2（BO3）4 were investigated. The absorption cross section oa is 3.11 × 10^-20cm2 at 808 nm. The absorption transition at 808 nm has an FWHM of 14 nm. The luminescence lifetime τf is 51.7 μs. The emission cross section oc at 1064 nm wavelength is 1.09 × 10^-19 cm2.

SYNTHESES AND SPECTROSCOPIC PROPERTIES OF PORPHYRIN-PHTHALOCYANINE MITH FLEXIBLE POLYATONIC CHAINS

The syntheses of porphyrin-phthalocyanine heterodimers with flexible polyatomic chains especially designed for the studies of intramolecular photoinduced processes are presented along with the effect of mutual orientation of the chromophore subunits on intramolecular energy transfer efficiency.

Synthesis,Crystal Structure,Spectroscopic Characterization,Thermal Stability and Magnetic Properties of a Dinuclear Copper(Ⅱ) Complex

A new copper（Ⅱ） complex [Cu2（MNA）2（2,2‘-bipy）2]·2.5H2 O with methy-5-norbornene-2,3-dicarboxylic acid（MNA） and 2,2’-bipyridine as ligands has been synthesized in the mixed solvents of DMF and water.It crystallizes in monoclinic,space group P 1,with a = 10.4191（11）,b = 12.8883（13）,c = 16.1114（16） A,α = 70.8090（10）,β = 80.568（2）,γ = 77.440（2）o,V = 1984.3（4） A^3,Dc = 1.551 g/cm^3,Z = 2,F（000） = 962,the final GOOF = 1.051,R = 0.0431 and w R= 0.0980.The crystal structure shows that the whole molecule consists of two independent dinuclear units,in which two copper ions are bridged by two μ2-η^1：η^0 3-carboxylate groups of MNA^2-.The coordination environment of Cu（Ⅱ） ion is Cu O3N2,giving a distorted square pyramidal geometry.The spectroscopic characterization,thermal stability and magnetic properties of the complex were investigated.

Spectroscopic Properties of Er^(3+)-Doped TeO_2-WO_3-ZnO-ZnF_2 Glasses

The Er^(3+)-doped TeO_2-WO_3-ZnO-ZnF_2(TWZOF) glasses were prepared. The absorption spectra, 1.5 μm emission spectra and fluorescence lifetimes of Er^(3+), excited at 970 nm, were measured. The J-O parameters Ω_ t (t =2, 4, 6), absorption and emission cross-sections were calculated. The dependence of the 1.5 μm emission intensity, fluorescence lifetime and bandwidth of the Er^(3+) emission upon the contents of ZnF_2 in glass were investigated. In TWZOF glass, Er^(3+) ions had a broad emission profile around 1.5 μm with the maximum FWHM of 83 nm. With the increasing of the content of ZnF_2, the emission intensity at peak wavelength and the fluorescence lifetime of Er^(3+) at 1.5 μm increase.

Spectroscopic Properties and Effect of Radiation Trapping of a New Er^(3+)/Yb^(3+) Co-Doped Tellurite-Silicate Glasses

A new serials of Er^3＋/Yb^3＋ co-doped tellurite-silicate glasses were prepared by the technique of high-temperature mehing. The thermal stability, absorption spectra, emission spectra and upconversion spectra were measured and investigated. It is found that these kinds of glasses have good thermal stability, broad FWHM and large stimulated emission cross-section. The three upconversion emission at 525, 546, 658 nm, corresponding to the ^2H11/2→^4Ⅰ15/2, ^4S3/2→4^Ⅰ15/2 and ^F9/2→^4Ⅰ15/2 transitions of Dr^3＋ ions,

Spectroscopic Properties of Nd^(3+)-Doped High Silica Glass Prepared by Sintering Porous Glass

A new kind of Nd^3＋-doped high silica glass （SiO2 〉 96% （mass fraction）） was obtained by sintering porous glass impregnated with Nd^3 ＋ ions. The absorption and luminescence properties of high silica glass doped with different Nd^3 ＋ concentrations were studied. The intensity parameters Ωt （t = 2, 4, 6）, spontaneous emission probability, fluorescence lifetime, radiative quantum efficiency, fluorescence branching ratio, and stimulated emission cross section were calculated using the Judd-Ofelt theory. The optimal Nd^3＋ concentration in high silica glass was 0.27% （mole fraction） because of its high quantum efficiency and emission intensity. By comparing the spectroscopic parameters with other Nd^3 ＋- doped oxide glasses and commercial silicate glasses, the Nd^3 ＋ -doped high silica glasses are likely to be a promising material used for high power and high repetition rate lasers.

Spectroscopic properties of Yb^(3+)-doped TeO_2–BaO–BaF_2–Nb_2O_5-based oxyfluoride tellurite glasses

A series of oxyfluoride glasses with the compositions of 75 mol% TeO2, 10 mol% Nb2O5, （15 mol%-x） BaO, x BaF2 （x =0 mol%, 5 mol%, 10 mol%, 15 mol%） doped with Yb2O3 were prepared by the melt-quenching method. Their emission cross-sections, fluorescence lifetimes, and gain properties were investigated by using the absorption spectra and the fluorescence decay curves. The results show that by substituting BaF2 for BaO, the emission cross-section decreases from 1.37 pm^2 to 1.21 pm^2, and the fluorescence lifetime increases from 0.71 ms to 0.96 ms. These properties indicate that this oxyfluoride tellurite glass may have potential uses as the Yb2O3-doped gain medium in a solid laser.

SYNTHESES AND SPECTROSCOPIC PROPERTIES OF LANTHANIDE COMPLEXES, Ln(acac)_3(Ph_3PO)_3

A series of new complexes of formula Ln(acac)_s(Ph_3PO)_3 (where Ln^(3+)=Nd^(3+), Sm^(3+), Eu^(3+), Tb^(3+), Ho^(3+)) have been prepared and characterized. The coordination of two ligands with lanthanide ions are studied by IR spectra, ~1H, ^(13)C, ^(31)P-NMR and metal-ligand charge tranafer tranaition is also discussed via electronic adaorption and luminescence spectroscopy.

Spectroscopic Properties of Nd^(3+)-Doped Tellurite Glasses

The Nd^3＋-doped pared. The absorption and tellurite glasses were preemission spectra of Nd^3 ＋- doped tellurite glasses at room temperature were measured. The Judd-Ofelt parameters （Ω2, Ω4, Ω6） of the glasses were calculated from measured absorption spectra. The calculation results of luminescence properties （A, β, τrad, σ） of Nd^3＋ ions in the tellurite were glasses were given. Spectroscopic properties, concentration quenching in these kinds of the glasses were investigated. The results indicate that the tellurite glasses with composition of 70% TeO2, 20% ZnO, （ 10 - x ） % La2O3, x % Nd2O3 （ mol% ） show high emission cross section and low phonon energy. The fluorescent intensity and the emission cross section have a maxi- mum value at x = 0.5, namely, the optimum Nd^3 ＋ ion concentration in the tellurite glass is 0.5% （1.93 × 10^20 ions·cm^-3）. The fluorescence properties of Nd^3＋ measured are basically in accord with the calculated results.

Synthesis, Crystal Structure and Spectroscopic Properties of N,N′-Diphenyl-N,N′-bis(2-fluorophenyl)-1,1′-biphenyl-4,4′-diamine

A fluorinated tetraphenylbenzidine derivative, N,N′-diphenyl-N,N′-bis（2-fluorophenyl）-1,1′-biphenyl-4,4′-diamine （C36H26F2N2, Mr = 524.59） was synthesized via the palladiumcatalyzed Buchwald-Hartwig reaction of N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine with 2-fluoroiodobenzene （yield： 75%） and structurally characterized. It crystallizes in monoclinic, space group P21/n with a = 9.820（7）, b = 14.305（11）, c = 10.233（8） , β = 108.973（9）o, V = 1359.3（18） 3, Z = 2, Dc = 1.282 g/cm3, μ（MoKα） = 0.084 mm-1, F（000） = 548, S = 1.018, the final R = 0.0439 and wR = 0.0928. It presents a linear centrosymmetric framework constituted by a linkage of biphenyl as a bridge and two fluorinated diphenylamine moieties. The UV-Vis absorption and fluorescence spectra of the title compound were also investigated. This compound emits intense blue fluorescence with a peak wavelength of 406 nm in film.