Characterization, crystal structure and luminescence properties of a new europium(Ⅲ) complex with macrocyclic ligand derived from 2,6-diformyl-4-methylphenol and diethylenetriamine

The title compound (13,27-dimethyl-3,6,9,17,20,23-hexaazatricyclo-[23.3.1.111,15]-triaconta-1(29),2,9,11,13,15(30),16,23,25,27-decaene-29,30-diol-N3, N6, N9, O29, O30)-bis (nitrato-O,O')-europium (Ⅲ) nitrate hydrate ([EuL(NO3)2(NO3).H2O, L denotes the macrocyc-lic ligand) was prepared and characterized by elemental analysis, infrared spectra, and electrospray mass spectra. Its crystal and molecular structure was determined by X-ray diffraction. The crystal crystallized in the monoclinic system, space group C2/c with a=2.3757 (4) nm, b=1.4302(3) nm, c=1.9584(3) nm, β=91.654(5)°, M=S18.60, V=6.651(2) nm3, Z=8,D=1.635 g/cm, F(000)=3312, R=0.0542, wR=0.1045. The central ion Eu3+ was nine-coordinated in the coordinaton geometry of a distorted tricapped trigonal prism. The macrocycle was coordi-nated through two oxygen and three nitrogen atoms. Two nitrate are chelate in the opposite positions of the macrocycle, the third nitrate be-ing ionic. At room temperature, excitation of the title complex gave rise to the characteristic emissions of the Eu3+ ion.     

Synthesis,crystal structure,and fluorescence of two dimeric europium（Ⅲ） complexes with 2-（trifluoromethyl）benzoate

Two complexes [Eu2（2-TFMBA）6（2,2′-bipy）2]·2H2O （1） and Eu2（2-TFMBA）6（1,10-phen）2 （2） （2-TFMBA=2-（Trifluoromethyl） benzoate; 2,2′-bipy=2,2′-bipyridine; 1,10-phen= 1,10-phenanthroline） were synthesized by solvent method and determined by X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system with space group P21/c, whereas complex 2 crystallizes in triclinic system with space group Pi. Both are binuclear molecules with an inversion center. In complex 1, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in bidentate-bridging mode. Each Eu^3＋ ion is eight-coordinated with six O atoms from five 2-TFMBA ligands and two N atoms from one 2,2′-bipy molecule. In complex 2, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in two modes, namely, bidentate-bridging and tridentate-bridging. Each Eu^3＋ ion is nine-coordinated with seven O atoms from five 2-TFMBA ligands and two N atoms from one 1,10-phen molecule. The two complexes both exhibited strong red fluorescence under ultraviolet light, and the ^5D0→^7Fj （j=0-4） transition emissions of Eu^3＋ ion were observed in their emission spectra.     

Synthesis, Characterization and Activity of Rare Earth Complexes with Schiff Base From 2,6-Diformylpyridine N-Oxide and 4-Amino-antipyrine

Six new rare earth complexes with Schiff base from 2,6-diformylpyridine N-oxide and 4-amino-antipyrine were synthesized. These complexes with general formula REL(NO3)3(RE = La, Pr, Eu, Tb, Er, Y) were characterized by elemental analysis, IR, UV, molar conductance measurements and antimicrobial activity.     

Synthesis and luminescence properties of rare earth ternary complexes consisting of Eu（Ⅲ）, β-diketones and 1,10-phenanthroline

Three novel β-diketones （HPPP, HTPP, and HFPP） ligands were synthesized by Sonogashira coupling reaction and Claisen condensation. The structure of β-diketones was confirmed with elemental analysis, IR, NMR and MS spectra. Three new ternary complexes consisting of Eu（Ⅲ）, β-diketones, and 1,10-phenanthroline（phen） were synthesized and characterized as TbL3phen （L=PPP, TPP, FPP） with elemental analysis, chemical analysis, and IR spectra, and their luminescence properties were studied.     

Synthesis, Structure and Photoluminescent Properties of A Novel Oxadiazole-Functionalized Europium（ Ⅲ ） Complex

Scheme1Synthesisrouteof2benzamide5phenyl[1,3,4]oxadiazole(HL1)andgaveabuffersolution.After2h,thesolutionwas pouredintowater;andthewhiteprecipitatewascol lectedanddriedundervacuum.PureproductHL1was obtainedbyre crystallizationfromethanol,m.p.211～213℃.Ana…     

Hydrothermal synthesis, crystal structure and magnetic properties of a Dy~Ⅲ-Fe~Ⅲ heteronuclear complex

A new 3d-4f heteronuclear complex [Fe(phen)3]2[FeDy(H2O)(tiron)3]·6H2O (1,Na2H2tiron=disodium 4,5-dihydro-xybenzene-1,3disulfonate) was synthesized by the hydrothermal reaction. The complex crystallized in the cubic system, space group P213 with the cell parameters:a=2.18786(14)nm, V=10.4727(12)nm3 , Z=4, F(000)=4720, R1=0.0493, wR2 =0.1165, S=1.05. In each [FeDy(H2O)(tiron)3]6-unit, it was revealed that the Fe3+ ion was in a FeO6 distorted trigonal anti-prism coordination polyhedron completed by six phenolate O atoms from three tiron 4- ligands, while Dy3+ in a DyO7 distorted monocapped trigonal anti-prism coordination polyhedron completed by three phenolate μ2-O atoms and three O atoms from sulfonate groups of three ligands and one O atom from water. The magnetic properties of the complex was determined in the range of 2-300K, indicating the antiferromagnetic interaction between the central DyIII-FeIII ions.     

Synthesis,structure and radiative and nonradiative properties of a new Dy3+ complex with sulfonylamidophosphate ligand

In recent years there has been growing interest in lanthanide-based multifunctional materials that exhibit interesting photophysical properties. This work presents spectroscopic and crystallographic characterization of a new dysprosium complex with sulfonylamidophosphate ligand. The crystal structure of [NaDy(SP)₄]₂·i-PrOH was determined and refined. It turns out that the Dy(III) complex is not isostructural with earlier reported compounds and crystallizes in the monoclinic system (space group P2₁). Two crystallographically independent dysprosium atoms are in eight-fold coordination, with a triangular dodecahedron geometry. Absorption, emission (77 and 300 K) and excitation spectra as well as fluorescence decay time measurements allowed optical characterization of obtained complex. Efficient energy transfer from SP^– ligand to Dy³⁺ ion has been demonstrated. The Judd-Ofelt theory was applied to predict fundamental fluorescence properties of Dy³⁺ ion in the title chelate. The Judd-Ofelt intensity parameters were used to determine the emission transition probabilities, fluorescence branching ratios and radiative lifetime of the emitting ⁴F_9/2 level. The obtained results indicate that the investigated chelate can be a potential candidate for OLEDs emitting yellow light.     

Synthesis, Characterization and Crystal Structure of Quaternary Complex of Gadolinium （Ⅲ）

Ａｎｕｍｂｅｒｏｆｌａｎｔｈａｎｉｄｅｔｅｒｎａｒｙｃｏｍｐｌｅｘｅｓｃｏｎ ｔａｉｎｉｎｇｈｅｔｅｒｏｃｙｃｌｉｃａｍｉｎｅｓｈａｖｅｂｅｅｎｒｅｐｏｒｔｅｄｓｉｎｃｅ1960 [1] .Ｉｎｒｅｃｅｎｔｙｅａｒｓｍｕｃｈａｔｔｅｎｔｉｏｎｈａｓｂｅｅｎｐａｉｄｔｏｑｕａｔｅｒｎａｒｙｃｏｍｐｌｅｘｅｓｏｆｌａｎｔｈａｎｉｄｅｓｂｅｃａｕｓｅｏｆｉｎ ｔｅｒｅｓｔｉｎｇｓｔｒｕｃｔｕｒｅ ,ｃｏｏｒｄｉｎａｔｉｏｎｍｏｄｅ ,ｃｏｍｐｅｔｉｔｉｏｎｒｅ ａｃｔｉｏｎａｎｄｐｒｏｐｅｒｔｙ[2～ 9] .ＥＳＲｃａｎｅ…     

Synthesis, structure and photoluminescent properties of a new Eu(Ⅲ) complex with 5-bromoisophthalic acid

The self-assembly of 5-bromoisophthalic acid (H2BIPA) with Eu(NO3)3·6H2O under the hydrothermal conditions gave a 3D coordination polymer, Eu2(BIPA)3(CH3CH2OH) (1), which was characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 displayed an unusual three-dimensional network of a rare (4,6)-connected (48.66.8)2(44.62)2(42.84) topology, which was different from Eu2(BDC)3(H2O)2 (BDC=isophthalate), because the -Br substituent of the isophthalate resulted in the different electronic effects and the steric hindrance to change the coordination modes of carboxylate groups in the assembled process. Moreover, the luminescent properties of 1 were also investigated in the solid state.     

Synthesis, Characterization and Luminescence Properties of Rare Earth Complexes with Bis （Pyridinyl-Amide）

A ligand, N^1, N^4-di （ pyridin-2-yl ） succi- namide （L） and its lanthanide（ IH ） complexes （RE = La, Eu, Tb, Gd, Yb ） were synthesized and characterized in detail. The results indicate that the composition of the binary complexes is determined as [ REL （H2O）2（NO3）2] NO3, that the complexes are 1 ： 1 electrolytes in DMF, and that the Tb^3＋ complex has brightly green fluorescence in a solid state. At the same time, the energy levels of the excited triplet states for the six ligands were determined to be 22989 -1 cm . The fact that the ligand sensitize Tb^3＋ complexes was explained by the relative energy gap between the lowest triplet energy level of the ligand （T） and ^5Dj of Tb^3＋ or Eu^3＋ . When 2000 cm^-1 〈 △E（T-^5D4） 〈 3000 cm^-1, the luminescent intensity of the Tb^3＋ complex is stronger. When 3000 cm^-1〈 △E （T-^5D1）, the luminescent intensity of the Eu^3＋ complex is weak- er or close to nil. This means that the triplet energy level of the ligand is a chief factor that dominates RE^3＋ luminescence.     

Hydrothermal synthesis, crystal structure and luminescence of a europium complex with phenylmalonic acid and 1, 10-phenanthroline

A new complex Eu2（PA）6（phen）2 was prepared with hydrothermal reaction using EuCl3.6H2O, phenylmalonic acid （H2phma）, and 1, 10-phenanthroline （phen）, where PA was the decarboxylated product of HEphma, phenylacetate. The crystal structure of the title complex was determined with the X-ray diffraction. The title complex was a binuclear molecule with an inversion center. Each Eu^3＋ ion was nine-coordinated with two nitrogen atoms from one phen molecule and seven oxygen atoms from five PA ligands. The carboxylic groups were bonded to the Eu^3＋ ion in three modes, the chelating bidentate, the bridging bidentate, and the bridging-chelating tridentate. The complex emits intense red fluorescence under ultraviolet light. The luminescence peaks correspond to the characteristic emission 5D0→7FJ （J=0-4） transitions of the Eu^3＋ ion.     

Synthesis, crystal structure and fluorescence of a new europium complex with 2-bromobenzoate and 2,2′-bipyridine

A new complex of {[Eu2(2-BrBA)6(2,2'-bpy)2]2.CH3CH2OH·H2O} (2-BrBA=2-bromobenzoate; 2,2'-bpy=2,2'-bipyridine) was prepared by solvent method and characterized with X-ray single-crystal diffraction, IR spectroscopy, UV spectrscopy, and fluorescence spectroscopy. The complex crystallized in triclinic crystal system, PT space group, with a=1.17196(4) nm, b=-2.36142(9) nm, c=2.59151(9) nm, a=113.266(2)°, β=101.100(2)°, and γ=94.400(2)°. Two independent dinuclear molecules were contained in the asymmetric unit. The two molecules were similar to each other. Each Eu(Ⅲ) ion was nine-coordinated with seven oxygen atoms from five 2-BrBA ligands and two ni-trogen atoms from 2,2'-bpy molecule. The carboxylate groups acted as bidentate-chelating, bidentate-bridging and chelating-bridging coor-dination modes. The complex adopted a distorted monocapped square-antiprism coordination geometry. Five peaks at 579, 591, 613, 652,and 697 nm appeared in the fluorescence spectrum, corresponding to 5D0→7F0, 5D0→7F1, 5D0→7F2, 5D0→7F3, and 5D0→7F4 transition emis-sions of the Eu(Ⅲ) ion, respectively.     

Synthesis,crystal structure and fluorescence property of 1-D europium complex with 2,3-difluorobenzoate

A new chain europium complex [Eu(2,3-DFBA)3·(H2O)2]n(2,3-DFBA=2,3-difluorobenzoate) was synthesized by solvent method.X-ray single-crystal diffraction analysis revealed that Eu3+ ions were linked through 2,3-DFBA groups via alternate bidentate-bridging and tridentate chelating-bridging coordination modes to form a one-dimensional(1-D) polymeric chain.Each Eu3+ ion is eight-coordinated by six O atoms of five 2,3-DFBA ligands and two water molecules.The abundant hydrogen bonds between chains resulted in a two...     

Synthesis, crystal structure and photophysical properties of a neodymium trifluoroacetate complex with 2,2'-bipyridine

The neodymium trifluoroacetate complexes were synthesized and characterized by single-crystal X-ray diffraction for [Nd(CF3COO)3·Bpy·(H2O)3]Bpy(1),elemental and TG analysis,FT-IR spectra,and PL spectra for Nd(CF3COO)3·Bpy(2)(Bpy:2,2’-bipyri-dine).The most interesting feature of the crystal structure for 1 is that it comprises a coordinated 2,2’-bipyridine molecule and an out-sphere 2,2’-bipyridine molecule.At the same time,the C-O distances appeared average which indicates the three atoms of carboxylato forming elec-tron-conjugate system.Hydrogen bond and π-π-stacking link the binuclear to two-dimensional sheet.The optical spectra for 2 exhibited that the complex possessed typical Nd(III) ion absorption and photoluminescence emission.The emission cross-section of 4F3/2→4I11/2 fluores-cence transition(3.63×10-20 cm2) was comparable with some laser glasses,which indicated good radiative properties of this neodymium trifluoroacetate complex in liquid matrix.The thermal analysis indicated that it was quite stable to heat.     

Synthesis, Characterization and Crystal Structure of Neutral Homoleptic Lanthanide Amide Yb(NPh_2)_3(THF)

Ｌａｎｔｈａｎｉｄｅａｍｉｄｅｃｏｍｐｌｅｘｅｓａｒｅａｎｉｍ ｐｏｒｔａｎｔｃｌａｓｓｏｆｐｒｅｃｕｒｓｏｒｓｆｏｒｌａｎｔｈａｎｉｄｅｄｅｒｉｖａｔｉｖｅｓ .Ｉｔｃａｎｂｅｅａｓｉｌｙｔｒａｎｓｆｏｒｍｅｄｔｏｃｏｒ ｒｅｓｐｏｎｄｉｎｇｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｂｙｒｅａｃｔｉｎｇｗｉｔｈｉｎｖｏｌｖｉｎｇｐｒｏｔｉｃｒｅａｇｅｎｔｓ[1,2 ] .Ｔｈｅｌａｎｔｈａｎｉｄｅａｍｉｄｅｕｓｅｄａｓｓｙｎｔｈｅｔｉｃｐｒｅｃｕｒｓｏｒｉｓｎｅｕｔｒａｌｈｏｍｏｌｅｐｔｉｃｃｏｍｐｌｅｘ ,ｏｔｈ…     

Synthesis, Characterization and Crystal Structure of Neutral Homoleptic Lanthanide Amide Yb（NPh2）3（THF）2

A neutral homoleptic lanthanide amide Yb(NPh2)3(THF)2 was obtained by reaction of anhydrous YbCl3 with LiNPh2 in THF. The product was characterized by elemental analysis, infrared spectrum and X-ray crystallographic analysis. The crystal data are monoclinic, P21/n space group, a=1.2052(2) nm, b=1.9369(3) nm, c=1.6523(2) nm, β=92.79(1)°, V=3.8524(9) nm3, Z=4, Dc=1.417 g*cm-3, μ=24.67 cm-1 (Mo Kα), F(000)=1668, R=0.036, Rw=0.039. The central metal ytterbium is coordinated by three terminal NPh2 groups and two THF molecules to form a five-coordinate distorted trigonal bipyramid. The mean Yb-N bond length is 0.2219(6) nm.     

A 4d-4f heterometallic coordination polymer： Synthesis, crystal structure and near-infrared luminescent properties

A 4d-4f heterometallic coordination polymer, [AgNd(pydc)2]?2H2O (1) (H2pydc=pyridine-3,4-dicarboxylic acid), was synthesized under hydrothermal conditions, and further characterized by elemental analysis, IR, thermogravimetric analysis and single-crystal X-ray dif-fraction. Complex 1 featured a three-dimensional (3D) framework containing one-dimensional (1D) channels occupied by free water molecules, which was constructed from 1D inorganic heterometallic chains and linear pydc linkers. To our knowledge, complex 1 represented a rare example of 3D open-framework 4d-4f heterometallic coordination polymer. After removal of the water molecules from complex 1, the remaining material had high thermal stability. Moreover, the near-infrared luminescent properties of 1 were also investigated in the solid state.