Synthesis, Crystal Structure of [ （MeC5H4）2Ln（μ-OCH2 CH2NMe2 ） ]2 （Ln = Sm, Y, Nd） and Their Catalytic Activity for Ring-Opening Polymerization of ε-Caprolactone

Reaction of (MeC5H4)3Ln with HOCH2CH2NMe2 in tetrahydrofuran (THF) gives the new complexes [ (MeC5H4)2Ln(μ-OCH2CH2NMe2)]2(Ln = Sm, Y, Nd) with nitrogen functionalized μ-alkoxide ligand. The complexes were characterized by elemental analysis and IR, and [ (MeC5H4)2Sm(μ-OCH2CH2NMe2)]2 was structurally characterized by the X-ray diffraction to be a dimer formed by two unsymmetric oxygen bridges. The complex has a tricyclic skeleton with the additional two Sm- N bonds via intmmoleeular coordination of OCH2CH2NMe2. The coordination number of the central metal Sm is nine. The tide complexes show good catalytic activity for ring-opening polymerization of ε-capmlactone.     

Polymerization of Dimethylaminoethyl Methacrylate Catalyzed by Substituted Indenyl Lanthanide（Ⅱ） Complexes

The polymerization of dimethylaminoethyl methacrylate （DMAEMA） catalyzed by the 1-cyclopentylindenyl lanthanide （Ⅱ） complex （1-C5H9C9H6）2Yb （THF）2 was investigated. The results indicated that the complex （1- C5H9C9H6）2Yb （THF）2 as a single component catalyst showed high activity. The conversion of the polymerization and the molecular weight of the polymer were affected by temperature, time, amount of catalyst and solvent in the polymerization process. The catalytic activity of （1-C5H9C9H6）2Yb （THF）2 enhanced significantly when a small amount of polar solvent THF was added into the polymerization system in which toluene was selected as the solvent. The optimal temperature of polymerization was about 0 ℃. Other modified substituted indenyl lanthanide （Ⅱ） complexes also showed good catalytic activity. The order of catalytic activity of the complexes was as follows： （1-C5H9C9H6）2Sm（THF）≈ （1- C2 H5 C9H6 ）2 Sm（THF）2 〉 （1 -C5 H9 C9 H6 ）2 Yb（THF）2 〉 （1 -PhCH2 C9 H6 ）2 Sm（THF）2. The steric regularity of p oly （dimeth- ylaminoethyl methacrylate） （PDM AEM A） was characterized by 1H NM R spectra. The polymerization provided syndio- tacticity-rich PDM AEM A. The molecular weight and the molecular weight distribution of PDM AEM A were measured by gel permeation chromatography.     

Polymerization of ε-caprolactone by lanthanide trisborohydrides and crystal structure of [Ce（BH4）2（THF）5] [Ce（BH4）4（THF）2]

Complexes of lanthanide trisborohydrides, formally Ln(BH4)3(THF)n (Ln=La, Ce, Sm, Yb), were synthesized and their catalytic activity for polymerization of ε-caprolactone was studied. All the complexes can catalyze this polymerization. It was found that the catalytic activities decreased in the order of La>Ce>Sm>Yb. The crystal structure of cerium trisborohydride was determined for the first time by single crystal X-ray diffraction analysis. It is an ionic pair complex of [Ce(BH4)2(THF)5][Ce(BH4)4(THF)2]. The cationic part involves two η3-BH4 ligands, while the anionic part involves two η3-BH4 groups and two η2-BH4 groups.     

Synthesis and crystal structure of [Y(C_5Me_4SiMe_3){μ-O(CH_2)_3CH_3}{N(SiHMe_2)_2}]_2

A dimeric yttrium complex [Y(C5Me4SiMe3){μ-O(CH2)3CH3}{N(SiHMe2)2}]2 (1) was isolated as one of the byproducts from the reaction of Y{N(SiHMe2)3}3(THF)2 with C5Me4HSiMe3 in 1:1.1 molar ratio in toluene at 100 C for 2 d.Complex 1 was characterized by elemental analysis,NMR spectroscopy,FT-IR spectroscopy,and X-ray single crystal structure analysis.X-ray diffractions revealed that com-plex 1 was a symmetric dimer,and the center metal Y3+ was six-coordinated by one nitrogen atom from the amide group,two bridgi...     

Synthesis and Crystal Structure of A Bimetallic Terbium Complex Tb2 {μ-CH2 SiMe2 NC6 H3 ^iPr2 -2, 6}3 （THF）3

The reaction of 2, 6-^iPr2CbH3NHSiMe3 with Tb（CH2SiMe3）3（THF）2 in benzene at room temperature afforded a binuclear terbium complex Tb2 {μ-CH2 SiMe2 NC6 H3 ^iPr2 -2, 6}3（THF）3. X-ray diffraction revealed that Tb atoms were bridged by three methylene units. One Tb atom was six-coordinated by two nitrogen atoms, three methylene carbons, and one THF molecule, while the other Tb atom was six-coordinated by one nitrogen atom, three methylene carbons, and two THF molecules. Both Tb atoms adopted a distorted trigonal prism geometry.     

Synthesis, structure and catalytic behavior of ytterbium complexes bearing a phenoxy（quinolinyl）amide ligand

Two ytterbium complexes stabilized by phenoxy(quinolinyl)amide ligand 3,5-Bu t 2 -2-OC 6 H 2 CH 2 N-8-C 9 H 6 N (L) were synthesized and characterized. Reaction of anhydrous YbCl 3 with 1 equiv. of LLi 2 in THF gave the ytterbium chloride [LYbCl(THF)] 2 (1) in 73% yield. A further reaction of complex 1 with equimolar of NaN(SiMe 3 ) 2 in THF afforded the unexpected heterobimetallic "ate"-complex L 2 YbNa(THF) 2 (2) via a ligand redistribution reaction. Complex 2 could also be prepared in high isolated yield by the reaction of anhydrous YbCl 3 with 2 equiv. of LNa 2 generated in situ. Both complexes 1 and 2 were characterized by IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction analysis. It was found that complex 2 was an effective catalyst for the addition reaction of aromatic amines to carbodiimides.     

Luminescent and Thermal Properties of Sm^ 3＋ Complex with Salicylate and o-Phenanthroline Incorporated in Silica Matrix

A ternary Sm（ Ⅲ ） complex with salicylate （sal-） and o-phenanthroline （phen） was synthesized and incorporated in silica matrix by sol-gel method. The luminescence behavior of the complex in silica gel was studied compared with that of the pure complex by means of emission, excitation spectra and thermogravimetic analysis. The results indicate that the fluorescence intensity ratio of the ^4G5/2→^6H9/2 transition to the ^4G5/2→^6H5/2 transition in silica gel doped with Sm（sal）3 （phen） is lower than that of the pure Sm（sal）3（phen）. The thermal stability of Sm（sal）3（phen） is enhanced greatly by the introduction of the complex into silica matrix. An isolated and chemical inert environment of the complex appears to be responsible for the thermal stability enhancement in silica gel.     

Synthesis and characterization of terbium（Ⅲ）-pyromellitic acid（H4L）-1,10-phenanthroline （phen） luminescent complex

The terbium(Ⅲ)-pyromellitic acid(H4L)-1,10-phenanthroline(phen) luminescent complex was synthesized using a co-precipitation method.The chemical composition of the synthesized complex was speculated to be Tb4L3(phen)0.075·10H2O by elemental analysis,inductively coupled plasma-atomic emission spectroscopy(ICP-AES),and Fourier-transform infrared spectroscopy(FT-IR).The X-ray diffraction analytic results indicated that the synthesized complex is a new crystalline complex,whose structure was different from those of other two ligands.The scanning electron microscopy analytic results showed that the product was of spherical crystals with good dispersion property,and the mean diameter of the spheres was about 1-2 μm.The TG-DTA result showed that the complex had good stability below 489 °C.PL spectra showed that the complex emitted characteristic green fluorescence of Tb(Ⅲ) ion under ultraviolet excitation.     

Synthesis, X-ray structure and luminescent properties of Sm^3＋ ternary complex with novel heterocyclic β-diketone and 1,10-phenanthroline （Phen）

A new neutral ternary samarium complex Sm(Phen)HL3 in which Phen is 1,10-phenanthroline and HL is (1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)-1,3-propanedione) was synthesized. Molecular structure of this complex was determined by X-ray diffraction. Under UV-light this complex is demonstrated bright red luminescence (λmax=647 nm), which was corresponding to the electric dipole 4G5/2→6H9/2 transition in Sm3+ ion. UV-absorption, excitation and emission spectra of the title compound were investigated.     

Synthesis,crystal structures of novel complexes of rare earth with norfloxacin,interaction with DNA and BSA

Three novel rare earth complexes [N(CH 3) 4 ][Ln(NF) 4 ]·6H 2 O(Ln=Nd(III)(1),Sm(III)(2),Ho(III)(3)) were synthesized using hydrothermal method from norfloxacin HNF=1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid,C 16 H 18 FN 3 O 3),imidazole and rare earth nitrates.The complexes were characterized by elemental analysis,FT-IR,TG-DTG and X-ray single crystal diffraction.Each rare earth ion was eight-coordinated with carboxyl-O atoms and keto-O atoms from norfloxacin.Four of the norfloxacin ions acted as bidentate chelate group took part in the coordination with rare earth ion.The structures of complexes were tetragonal system with space group I4 1 /acd,which were allomerism.The interaction between complex 1 and DNA was studied by electronic absorption spectra and fluorescence spectroscopy.The binding interaction between the complex 1 and bovine serum albumin(BSA) was studied by fluorescence spectroscopy.The complex 1 bound to DNA by the mode of partial intercalation.Complex 1 had a strong ability to quench the fluorescence from BSA.The complex interaction was mainly a static quenching process with BSA together with formation of two binding sites.     

Synthesis and characterization of lanthanide complexes containing a bulky tridentate [N,N,O] Schiff base ligand

The lanthanide complexes containing a bulky tridentate [N,N,O] Schiff base ligand 3,5-But2-2-(OH)C6H2CH=N-8-C9H6N (HL) were synthesized and characterized. The reaction of anhydrous LnCl3 with NaL formed in situ in a 1:1 molar ratio in THF at room temperature afforded the lanthanide Schiff base dichloride complexes LnLCl2(DME) (Ln=Eu (1);Sm (2)). Complexes 1 and 2 can be used as precursors for the synthesis of the lanthanide cyclopentadienyl Schiff base derivatives. The reactions of complexes 1 and 2 with one equiv of NaCH3C5H4 in THF provided the desired products LnL(CH3C5H4)Cl(THF)·THF (Ln=Eu (3);Sm (4)) in good isolated yields. These complexes were characterized by elemental analysis, IR spectra, and X-ray structural determination, in the case of complexes 3 and 4. The crystal data of complex 3 are monoclinic, P21/c space group, a=1.3370(2) nm, b=1.5190(2) nm, c=1.8910(3) nm, β=109.846(4)°, V=3.6125(8) nm3, Z=4, Dc=1.416 mg/m3, μ=1.847 mm-1, F(000)=1584, R=0.0707, wR=0.1350. The crystal data of complex 4 are monoclinic, P21/c space group, a=1.3383(1) nm, b=1.5210(2) nm, c=1.8960(2) nm, β =109.878(3)°, V=3.6293(7) nm3, Z=4, Dc=1.407 mg/m3, μ=1.728 mm-1, F(000)=1580, R=0.0670, wR=0.1385.     

Synthesis of 2, 6-Bis（1＇-Phenyl-3＇-Methyl-5＇-Oxopyrazole-4＇） Pyridinediacyl and Its Solid-Liquid Extraction Behavior for Ce（Ⅲ）

β-diketone type chelating ligands have high coordinative activity and selectivity, and are widely applied in analytical ehemistry. In order to obtain profounder understanding to the properties of bis(4-aeylpyrazolone-5), A new 4-aeylpyrazol-5-one derivative (H2BPMPP) was syntheszed, whieh eontains a heteroeyelie ring between two 1-phenyl-3-methyl-4-aeylpyrazol-5-one rings. The new compound was eharaeterized by element analyses, UV, IR and ^1H NMR speetra. The equilibrium of the keto-enol tautomerism was studied. The results show that a lower dieleetric constant of solvent favors the enol form whieh has a higher λmax.Due to speeial merits of paraffin wax, the solidliquid extraetion behavior of Ce(Ⅲ) with molten paraffin wax as a diluent was also investigated at higher temperature. The value of the pH1/2 was 3.19 and the value of logKex was 3.467. The ehemieal eomposition of the complex was obtained by the slope analysis method.     

Synthesis and luminescence properties of a novel red Sr3Bi（PO4）3：Sm^3＋ phosphor

A series of Sr3Bi1-x(PO4)3: xSm3+phosphors were prepared by solid state method at 1250 °C for 4 h. X-ray diffraction (XRD) indi-cated that the sample was of a pure phase of Sr3Bi(PO4)3. The main excitation peaks were located at 343 (6H5/2→4H9/2), 360 (6H5/2→4D3/2), 373 (6H5/2→6P7/2), 400 (6H5/2→4F7/2), 414 (6H5/2→6P5/2) and 467 nm (6H5/2→4I13/2). The main emission were located at 563 (4G5/2→6H5/2), 599 (4G5/2→6H7/2), 646 (4G5/2→6H9/2) and 708 nm (4G5/2→6H11/2). The intensest emission was excited by 400 nm. We studied the effect of differ-ent doping concentrations of Sm3+ activator on the luminescence properties and found that the luminescent intensity first increased with Sm3+ concentration increasing, and then decreased. The luminescent intensity had the best value when x=0.04. The chromaticity coordinates of the sample Sr3Bi0.96(PO4)3:0.04Sm3+ were (x=0.57, y=0.36), and the lifetime was 2.12 ms.     

Synthesis kinetics and thermophysical properties of La_2（Zr_（0.7）Ce_（0.3））_2O_7 ceramic for thermal barrier coatings

La2(Zr0.7Ce0.3)2O7 (LZ7C3) ceramic was synthesized by solid state reaction with La2O3, ZrO2 and CeO2 as starting materials. The synthesis kinetics, phase structure, mass loss and microstructure were studied by thermo gravimetric-different thermal analyzer (TG-DTA), X-ray difference (XRD) and scanning electron microscopy (SEM). The thermal conductivity and thermal expansion coefficient were measured by laser-flash method and pushing-rod method, respectively. XRD results showed that LZ7C3 was a mixture of La2Zr2O7 (LZ, pyro- chlore) and La2Ce2O7 (LC, fluorite). The lowest synthesis temperature and time of LZ7C3 were 1400 oC and 5 h. There were no peaks of La2O3 when the powder granularity was about 0.82 μm in the synthesis process. The atom ratio La:Zr:Ce of prepared LZ7C3 powder was very close to 10:7:3 which was the theory value of LZ7C3. The thermal conductivity of LZ7C3 decreased gradually with the temperature increased up to 1200 oC, and was located within 0.79 to 1.02 W/(m·K), which was almost 50% lower than that of LZ, whereas its thermal expansion coefficient was larger and the value was 11.6×10-6 K-1.     

Synthesis, Characterization, and Reactivity of Amine Bis（phenolato） Cyclopentadienyl Lanthanide Complexes

（C5H5）3Ln（THF）reacted with amine bis（phenol） LH2 [ L = Me2NCH2CH2N {CH2-（2-O-C6H2-But^1-3-Me- 5）}2 ] in a 1：1 molar ratio in THF to generate the amine bis（phenolato） cyclopentadienyl lanthanide complexes LLn（C5H5） （THF）·（THF）,（Ln = La （1）, n =0; Ln = Sm（2）, n = 1） in high yields. Complexes 1 and 2 were fully characterized by elemental analysis, NMR （for 1） and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P21/c space goup, a= 1.1595（1） nm, b = 1.8588（2） nm, c = 1.6647（1） nm, β = 98.490（2）°, V =3.5486（5） nm^3, Z =4, Dc = 1.338 mg· m^3,μ = 1240 mm^-1, F（000）= 1488, R =0.0249, wR = 0.0568. The crystal data of complex 2 are monoclinic, P21/c sp ace goup, a = 0.9692 （1） nm, b = 1.4583 （2） nm, c = 2.8192 （3） nm, = 96.805 （2）°, V = 3.9584 （7） nm^3, Z=4, Dc =1.340 mg · ma, μ = 1.524 mm^-1, F（000）= 1668, R =0.0346, wR =0.0756. The attempts failed to synthesize the amine bis（phenolate） lanthanide alkoxides by the reactions of complexes 1 and 2 with alcohols. The preliminary results revealed that complex 1 can initiate ε-caprolactone polymerization.     

Synthesis and Crystal Structure of a Novel Ion-pair Complex of [Li(THF)_4Nd(C_8H_8)_2]·2THF

The reaction of NdCl_3 with lithium methylnaphthalene in 1:2 mole ratio in THF generates black powder.The powder reacts with cyclooctatetraene(COT)in THF to form the title complex.[Li(THF)_4Nd(C_8H_8)_2]·2THF crystallizes in the monoclinic space group P2/c with unit-cell dimensions a=1.7858(7)nm,h=1.3243(4)nm,c=1.8086(6)nm.β=106.52(4)°,V=4.10 nm~3 and D_c=1.268 g/cm~3 for Z=4.F(000)=1660,R=0.0774,R_n=0.0733.The complex consists of discrete ion-pair and two THF moleculesadduct.In the anion,the neodymium atom is coordinated by two COT rings.The structure of the cation showsthat the lithium atom is attached with THF molecules only.     

Promotional effects of samarium on Co3O4 spinel for CO and CH4 oxidation

A series of Co3O4 spinel catalysts modified by Sm were prepared by co-precipitation method and tested for CH4 and CO oxidation.The addition of a small amount of Sm into Co3O4 led to an improvement in the catalytic activity for both reactions.Co0.98Sm0.02 and Co0.95Sm0.05,the two samples with Co/Sm molar ratio of 0.98/0.02 and 0.95/0.05 in sequence,showed the similar and the highest activity for CH4 oxidation,with CH4 complete conversion at 450 oC.In contrast,Co0.90Sm0.10 was the most active sample for CO oxidation,with CO complete conversion at 120 oC.The catalysts were characterized by techniques of N2 adsortion-desorption with Brunauer-Emmett-Teller technique(N2-BET),X-ray powder diffraction(XRD),thermal gravity analysis-differential scanning calorimetry(TGA-DSC),H2 temperature programmed reduction(H2-TPR) and X-ray photoelectron spectroscopy analysis(XPS).Compared with pure Co3O4,for Co1–x Smx catalysts with 0.02≤x≤0.10,the addition of a small amount of Sm resulted in the formation of spinel Co3O4 and amorphous SmCoO3,hence increasing the number of Co3+ and the active surface oxygen species,which was responsible for the improvement of the activity.Co0.95Sm0.05 catalyst showed not only high thermal stability and activity but also good reaction durability in the presence of 5% water vapor for CH4 oxidation.     

Thermochemical studies on complex of [Sm(o-NBA)_3phen]_2

A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔθ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle according to Hess’s Law, the standard molar enthalpy of formation of [Sm(o-NBA)3 phen]2 (s) was estimated to be f mHΔθ=–4109.2±7.3 kJ/mol.     

Hydrothermal synthesis and structural studies of a new coordination polymer of lanthanum(Ⅲ) with benzene-1,2,4,5-tetracarboxylic acid and 4,4''-bipyridine

A new lanthanum complex formulated as { (bpyH2)[La(btc)(H2O)4(NO3)]·2H2O }n (1) (btcH4=benzene-1,2,4,5-tetracarboxylic acid; bpy=4,4'-bipyridine) was hydrothermally synthesized. The complex was characterized by FT-IR spectroscopy, elemental analysis and X-ray diffraction. X-ray crystal structural analysis revealed that the compound belonged to the monoclinic space group C2/c with cell parameters a= 1.42806(7) nm, b=1.10258(5) ran, c=-1.60333(8) nm and β=101.9400(10)°. The complex was polymeric with La<Ⅲ atoms linked by four O atoms from two carboxylate groups of one benzene-1,2,4,5-tetracarboxylate. The LaⅢ atom was ten coordinated in a distorted tetracapped trigonal prism. In the crystal structure, a wide range of noncovalent interactions consisting of hydrogen bonding (of the types of O-H…O, N-H…O and C-H…O) and ion pairing interactions connected the various components into a supramolecular structure.     

Synthesis and fluorescence properties of Eu（Ⅲ）, Tb（Ⅲ） and Sm（Ⅲ） with β-diketone and 2,2＇- bipyridine

Three new rare earth ternary complexes,RE(PPP)3bpy(RE=Sm 3+ ,Eu 3+ ,Tb 3+ ),were synthesized by the reaction of 1-phenyl-3-(p-phenylethynylphenyl)-1,3-propanedione(HPPP)and 2,2′-bipyridine(bpy)with rare earth chloride RECl3,respectively,in alcohol solution. The compositions were characterized by means of infrared(IR)spectra,chemical analysis,elemental analysis,and thermodynamic analysis.Luminescent properties of the three complexes were studied.At room temperature,under UV light excitation,the Sm 3+ ,Eu 3+ and Tb 3+ complexes exhibited characteristic emission of the central ions.The fluorescence spectra showed that the fluorescence emission intensity of Eu 3+ complex was the strongest.The narrow strongest emission band of Eu 3+ complex was considered to be a valuable material with bright red fluorescence.