Thiocyanates of rare-earth elements with tetramethylphenanthroline

Molecular [M(NCS)₃(H₂O)(Me₄Phen)₂] · (Me₄Phen) · 0.75EtOH and anionic [H(Me₄Phen)][М(NCS)₄(Me₄Phen)₂] complexes are synthesized using thiocyanates М(NCS)₃ · 6H₂O (M = Y, Eu, Tb) and 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4Phen). The complexes are characterized by IR spectroscopy and elemental, X-ray phase, and X-ray diffraction analyses (CIF files CCDC no. 1498178–1498184). The thermoanalytical study shows that the solvate molecules Me₄Phen are localized in the internal coordination sphere of the molecular complexes at 195–250°C. The magnetic behavior of the Eu and Tb complexes is governed by the nature of the Ln ion.     

3-((4，6-二甲基-2-嘧啶基)硫代)-丙酸和菲咯啉三元稀土配合物的晶体结构和发光性能

制备了以3-((4,6-二甲基-2-嘧啶基)硫代)-丙酸(HL)和菲咯啉(Phen)为配体的2个三元稀土配合物[Eu(L)₃(Phen)]₂·2H₂O(1)和[Tb(L)₃(Phen)]₂·2H₂O(2),并对其结构进行了表征。单晶X射线衍射分析表明它们是同构的。2个稀土离子(Ln)由4个羧酸配体桥接,形成二聚体排列。其余2个羧酸配体和Phen以双齿螯合方式与Ln配位。Ln的配位数为9,具有扭曲的单端方形反棱柱配位多面体构型。固态光致发光测试表明,这2种配合物都显示了金属中心的特征发射带。     

Hydrothermal synthesis and structural characterization of three lanthanide coordination polymers with adipic acid and 1,10-phenanthroline

Three new lanthanide coordination polymers, [Ln(Ad)_3/2(Phen)] _n ·2nH₂O (Ln = Eu, 1; Pr, 2; Ad = adipate; Phen = 1,10-phenanthroline) and [Yb(Ad)_3/2(Phen)] _n ·nH₂O 3, were prepared by hydrothermal reactions. The structures of 1, 2 and 3 are reported. In compound 1, Eu(III) ions are bridged by adipate ligands in two modes into 2-D polymeric layers. Adjacent layers are assembled by hydrogen bonding and π–π stacking between 1,10-phenanthrolines into a 3-D supramolecular structure. Compound 2 is isostructural with 1. In compound 3, the Yb(III) ions are connected by adipate ligands in three modes into a 3-D network.     

Synthesis and crystal structure of Isotrithionedithiolato-bis(phenanthroline)zinc(II)

The synthesis of a mixed-ligand complex 1,3-dithiole-2-thione-4,5-dithiolato-bis(1,10-phenanthroline)zinc(II), [Zn(Dmit)(Phen)₂], is described. The crystals are monoclinic, space group P2₁/n, a = 11.868(2) Å, b = 13.122(3) Å, c = 17.010(3) Å, β = 102.01(3)°, Z = 4. The coordination polyhedron of the Zn(II) atom is an octahedron formed by two sulfur atoms of the Dmit ligand and four nitrogen atoms of the two Phen ligands. The complex is studied by IR and UV spectroscopy.     

A new 1D coordination polymer constructed by CaCl2 with 5-aminoiosphtalic acid (H2AIP) and 1,10-phenanthroline ligands using the water bath method

A new coordination polymer, [Ca(AIP)(Phen)(H₂O)₂] · Phen · H₂O (H₂AIP = 5-aminoisophthalic acid, Phen = 1,10-phenanthroline), was synthesized using the water bath method and characterized by elemental analyses and single crystal X-ray diffraction, which revealed that I has an interesting 1D chain structure. The adjacent chains are further connected together via the π-π packing interactions and hydrogen bonding interactions.     

3-((4，6-二甲基-2-嘧啶基)硫代)-丙酸和菲咯啉三元稀土配合物的晶体结构和发光性能

制备了以3-((4,6-二甲基-2-嘧啶基)硫代)-丙酸(HL)和菲咯啉(Phen)为配体的2个三元稀土配合物[Eu(L)₃(Phen)]₂·2H₂O(1)和[Tb(L)₃(Phen)]₂·2H₂O(2),并对其结构进行了表征。单晶X射线衍射分析表明它们是同构的。2个稀土离子(Ln)由4个羧酸配体桥接,形成二聚体排列。其余2个羧酸配体和Phen以双齿螯合方式与Ln配位。Ln的配位数为9,具有扭曲的单端方形反棱柱配位多面体构型。固态光致发光测试表明,这2种配合物都显示了金属中心的特征发射带。     

Synthesis,spectral characterization,crystal structures of lanthanide(III) pyrrolidine dithiocarbamate complexes and their catalytic activity

A series of lanthanide(III) pyrrolidine dithiocarbamate complexes [Ln(Pyrrol-Dtc)₃(Phen)] {Pyrrol-Dtc = pyrrolidine dithiocarbamate; Phen = 1,10-phenanthroline; Ln = La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III), Dy(III), Er(III)} have been synthesized and structurally characterized. The molecular structures of [La(Pyrrol-Dtc)₃(Phen)], [Pr(Pyrrol-Dtc)₃(Phen)], [Sm(Pyrrol-Dtc)₃(Phen)], and [Dy(Pyrrol-Dtc)₃(Phen)] have been confirmed using single crystal XRD studies. The results reveal that in these complexes, the central Ln(III) ion is coordinated to three Pyrrol-Dtc and one Phen and possesses a distorted dodecahedron geometry. Catalytic activity of these complexes in trimethylsilylcyanation reaction has been studied.     

Molecular and crystal structure of bis(1.10-phenanthroline)copper(I) (5-fluorouracil-1)-yl-acetate 3.25 hydrate

In the title compound, (Phen)₂Cu^I(C₆H₄FN₂O₄) · 3.25H₂O (Phen is 1,10-phenanthroline and C₆H₄FN₂O₄ is (5-fluorouracil-1)-yl-acetate), each Cu⁺ ion is five-coordinated by four basal N atoms and one oxygen atom, and the coordination geometry around each Cu⁺ ion is an irregular square pyramid. The crystals are orthorhombic, space group Pnma, with a = 13.080 (3), b = 16.023(4), c = 130.422(8) Å.     

Synthesis, crystal structure, and luminescence of a new complex [Co(6,6′-Bpbc)(Phen)(H2O)] · 2EtOH

A novel complex constructed with [Co(6,6′-Bpbc)(Phen)(H₂O)] · 2EtOH (6,6′-Bpbc = 2,2′-bipyridine-6,6′-dicarboxylic acid, Phen = 1,10-phenanthroline) has been successfully synthesized and characterized by X-ray diffraction, and elementary analysis. The photoluminescence properties of this complex were also studied. In the crystal, the cobalt(II) ion adopts the formation of a heptacoordination environment, and the structure units aggregate together to give birth to the infinite 1D chains, 2D-networks, and 3D-frameworks through either hydrogen bonding or π···π-stacking interaction between the aromatic rings.     

Synthesis and luminescence properties of neutral Tm(III), Dy(III), and Gd(III) complexes with 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)-1,3-propanedione and 1,10-phenanthroline

Neutral complexes of composition [LnL₃Phen], where Ln = Tm, Dy, and Gd, were synthesized by the reaction of LnCl₃ with heterocyclic diketone 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)-1,3-propanedione (HL, 1) and 1,10-phenanthroline in an aqueous alcohol solution in the presence of NaOH. The composition of the complexes was proved by elemental analysis. Their optical and luminescence properties were studied.     

Synthesis,structure, DNA-binding,and nuclease activity of a 3d–4f mixed metal nitrosyl complex, [Pr(phen)2(MeOH)(H2O)2][Fe(CN)5(NO)] · (Phen)(DMF)(MeOH)(H2O)

A cyano-bridged heterometallic lanthanide-transition metal nitrosyl complex, [Pr(phen)₂(MeOH)(H₂O)₂][Fe(CN)₅(NO)]?·?(Phen)(DMF)(MeOH)(H₂O) (Phen?=?1,10-phenanthroline and DMF?=?dimethylformamide), has been synthesized from reaction of PrCl₃?·?6H₂O with 1,10-phenanthroline in methanol and sodium nitroprusside followed by crystallization from DMF. The crystal structure shows that the complex is a 1-D chain, stabilized by coordination, hydrogen-bonding, and π–π stacking interactions. The complex shows nuclease activity with pUC19 supercoiled DNA in DMF/Tris-HCl buffer in the presence of H₂O₂.     

Crystal structure of (1,10-phenanthroline)ethylenediamine-<Emphasis Type="Italic">N,N′</Emphasis>-diacetatocopper(II) pentahydrate, [Cu(Edda)(Phen)] · 5H<Subscript>2</Subscript>O

The products of oxidation of ethylenediaminetetraacetic acid by manganese dioxide have been used to synthesize crystals of [Cu(Edda)(Phen)] · 5H₂O (Edda is ethylenediamine-N,N′-diacetate, and Phen is 1,10-phenanthroline). The X-ray diffraction analysis of the crystals shows that the N atoms of the Edda and Phen ligands lie in the equatorial plane around the Cu atom, and the O atoms of the Edda ligands are localized in more remote axial positions. The [Cu(Edda)(Phen)] complexes are grouped in pairs at a distance of 3.46 Å between the mean planes of the Phen ligands. Ten water molecules are united by hydrogen bonds into symmetric isolated clusters, and further they form a three-dimensional framework with the [Cu(Edda)(Phen)] complexes.     

Synthesis and characterization of a novel coordination polymer {[Mn(L)(Phen)<Subscript>2</Subscript>] · 2H<Subscript>2</Subscript>O}<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript><Superscript>1</Superscript>

A novel coordination polymer {[Mn(L)(Phen)₂] · 2H₂O} _n (I) has been synthesized by the reaction of Mn(CH₃COO)₂, 2,2′-bipyridine-5,5′-dicarboxylic acid (HL) and 1,10-phenanthroline (Phen). The structure of the complex was charactered by single-crystal X-ray diffractometry. The unit cell parameters for complex I: a = 11.796(3), b = 17.837(5), c = 15.081(4) Å; β = 101.804(5)°; V = 3106.0(15) ų; Z = 4; space group C2/c. The Mn(II) atom is coordinated by four nitrogen atoms from two Phen molecules and two oxygen atoms from two molecules L with a distorted octahedral geometry. Complex was dibridged by the L ligand forming a 1D infinite chain. Intramolecular weak interactions, such as hydrogen bonds and π...π-stacking, were found in the title complex, and 3D supramolecular framework was constructed by intermolecular weak interactions mentioned above.     

NMR and luminescence spectroscopy study of the formation of mixed europium β-diketonate complexes with trifluoroacetic acid in nonaqueous solutions

The ligand substitution in Eu(AA)₃ · Phen-CDCl₃-TFA systems, where AA is acetylacetone, Phen is 1,10-phenanthroline, and TFA is trifluoroacetic acid was studied at various molar ratios (m) of competing ligands (m = TFA/AA) using NMR (¹H, ¹⁹F) and luminescence spectroscopy. The formation of mixed Eu(AA)₂(TFA) · Phen and Eu(AA)(TFA)₂ · Phen complexes in the resultant solutions was attested. The luminescence spectra were studied. The competitive capacity of TFA was ascertained to be higher than that of AA. Depending on the m value, the substitution of acido ligands was shown to occur successively according equations Eu(AA)₃ · Phen + (TFA) _n = Eu(AA)_{3 − n} (TFA) _n · Phen + (AA) _n (n = 1, 2, 3).     

Application of rotate-bomb calorimeter for determining the standard molar enthalpy of formation of Ln(Pdc)3(Phen)

Thirteen solid ternary complexes Ln(Pdc)₃(Phen) (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;) have been synthesized in absolute ethanol by rare-earth element chloride low hydrate reacting with the mixed ligands of ammonium pyrrolidinedithiocarbamate (APdc) and 1,10-phenanthroline · H₂O (o-Phen · H₂O) in the ordinary laboratory atmosphere without any cautions against moisture or air sensitivity. IR spectra of the complexes showed that the Ln³⁺ ion was coordinated with six sulfur atoms of three Pdc⁻ and two nitrogen atoms of o-Phen · H₂O. It was assumed that the coordination number of Ln³⁺ is eight. The constant-volume combustion energies of the complexes, Δ_c U, were determined by a precise rotate-bomb calorimeter at 298.15 K. Their standard molar enthalpies of combustion, Δ_c H _m ^o , and standard molar enthalpies of formation, Δ_f H _m ^o were calculated. The text was submitted by the authors in English.     

Synthesis,structure and luminescence properties of two novel lanthanide complexes with 2-fluorobenzoic acid and 1,10-phenanthroline

Two lanthanide complexes with 2-fluorobenzoate (2-FBA) and 1,10-phenanthroline (phen) were synthesized and characterized by X-ray diffraction. The structure of each complex contains two non-equivalent binuclear molecules, [Ln(2-FBA)₃?·?phen?·?CH₃CH₂OH]₂ and [Ln(2-FBA)₃?·?phen]₂ (Ln?=?Eu (1) and Sm (2)). In [Ln(2-FBA)₃?·?phen?·?CH₃CH₂OH]₂, the Ln³⁺ is surrounded by eight atoms, five O atoms from five 2-FBA groups, one O atom from ethanol and two N atoms from phen ligand; 2-FBA groups coordinate Ln³⁺ with monodentate and bridging coordination modes. The polyhedron around Ln³⁺ is a distorted square-antiprism. In [Ln(2-FBA)₃?·?phen]₂, the Ln³⁺ is coordinated by nine atoms, seven O atoms from five 2-FBA groups and two N atoms of phen ligand; 2-FBA groups coordinate Ln³⁺ ion with chelating, bridging and chelating-bridging three coordination modes. The polyhedron around Ln³⁺ ion is a distorted, monocapped square-antiprism. The europium complex exhibits strong red fluorescence from ⁵D₀?→?⁷F _j ( j?=?1–4) transition emission of Eu³⁺.     

三价轻希土—PMBP—路易斯碱三元配合物的合成及其性质的研究

合成了1—苯基—3—甲基—4—苯甲酰基—吡唑啉酮—5(PMBP)和路易斯碱的三价轻希土三元配合物LnA_3·L(A=Pmbp~-;L=C_2H_5OH时,Ln=La、Pr、Sm、对Gd为GdA_3·(C_2H_5OH)_(0·25);L=Phen(邻菲罗啉)时,Ln=Pr-Gd,L=TBPO(三丁基氧化膦)时,Ln=La、Pr—Gd)。测定了它们的摩尔电导值、热谱、红外光谱、可见—紫外光谱、荧光光谱和质子核磁共振谱。观察到热稳定性次序为LnA_3·Phen>LnA_3·TBPO。从同类型配合物系列的热效应值、LnA_3·Phen型配合物的合成难易程度及其紫外最大吸收波长的移动可观察到镧系收缩现象。     

[Cu(Phen)_3][DTB]·6H_2O的合成与晶体结构

利用螯合配体1,10-邻菲咯啉(Phen)与2,2′-二硫代二苯甲酸(H2DTB)的钠盐及氢氧化铜反应合成了一种新型配合物[Cu(Phen)3][DTB].6H2O,通过元素分析、红外光谱和X射线单晶衍射等技术对其进行了表征.配合物属单斜晶系,空间群P2(1)/c,晶胞参数:a=1.822(2)nm,b=3.053(4)nm,c=2.016(3)nm,α=90°,β=106.28(4)°,γ=90°,Z=8,V=10.762(25)nm3,Dc=1.255 g/cm3,Mr=1016.57.该配合物晶体结构由配阳离子[Cu(Phen)3]2+和未配位的反荷阴离子[DTB]2-和晶格水分子组成.每个Cu(Ⅱ)原子与来自三个Phen的6个N原子配位,形成畸变的八面体结构单元.     

稀土配合物的研究 I: 镧系元素与4-酰代-双吡唑啉酮及1,10-二氮杂菲的混配配合物的合成及表征

用镧系硝酸盐与1,6-双(1'-苯基-3'-甲基-5'-氧代吡唑-4'-基)-1,6-己二酮(1,H2L)和1,10-二氮杂菲(2, Phen)在乙醇-水溶液中, 于PH5-6时合成了12种新的固态配合物Ln2L3Phen2. 4H2O(Ln=Pr, Nd, Sm-Lu)。用元素分析、水份及配体分析、红外、紫外,质子核磁共振、荧光光谱和热分析鉴定了所有的配合物, 从而推测, 可能L是四啮配体,Phen是二啮配体。     

Neodymium(III) tris(1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)propane-1,3-dionato)(1,10-phenanthroline): Synthesis and photophysical properties

The reaction of NdCl₃ with 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)propane-1,3-dione (HL) and 1,10-phenanthroline (Phen) in the presence of a base afforded complex [Nd(L)₃Phen] (I). Unstable solvate I · 2CH₂Cl₂ was obtained from a solution of the complex in dichloromethane, and its structure was determined by X-ray diffraction analysis. The photophysical properties of the complex were studied. Possible routes for the energy transfer in the course of photoluminescence were proposed.