系列Sm3+配合物的合成、结构及光物理性能

采用水热方法合成了4种Sm³⁺配合物, 即{[SmZn(2,5-pdc)₂(tp)_0.5(H₂O)]·2H₂O}_n(1), [Sm₂Zn₂(C₆H₅COO)₁₀(Imh)₂(H₂O)₂](2), {[Sm₂(NO₂C₆H₄COO)₆(H₂O)₄]·H₂O}_n(3)和{[SmN(CH₂COO)₃(H₂O)₂]·H₂O}_n(4)[2,5-pdc=2,5-吡啶二羧酸根, tp=对苯二甲酸根, C₆H₅COO=苯甲酸根, Imh=咪唑, NO₂C₆H₄COO=对硝基苯甲酸根, N(CH₂COO)₃=氨三乙酸根]. 通过单晶X射线衍射确定了其晶体结构. 在室温下测定了其红外光谱、 紫外-可见-近红外光谱以及在近红外区和可见区的发射光谱. 结果表明, 4种配合物在近红外区或可见区均出现Sm³⁺离子的特征发射. 这是形成配合物后, Zn-配体部分和配体对Sm³⁺离子发光的敏化作用所致. 此外, 讨论了不同有机配体或d过渡金属离子对Sm³⁺离子发光的影响, 并分析了配合物中Sm³⁺离子的近红外发射带位移、 劈裂和加宽的原因.     

Syntheses and structural characterization of transition metal(II) coordination polymers containing 4,4′-dipyridyldisulfide

The reactions of Zn(NO₃)₂ · 6H₂O and FeSO₄ · 7H₂O with 4-PDS (4-PDS = 4,4′-dipyridyldisulfide) and NH₄SCN in CH₃OH afforded the complexes [Zn(NCS)₂(4-PDS)]_n (1) and [Fe(NCS)₂(4-PDS)₂ · 4H₂O]_n (2), respectively, while the reaction of CoCl₂ · 6H₂O with 4-PDS in CH₃OH gave the complex {[Co(4-PDS)₂][Cl]₂ · 2CH₃OH}_n, (3). These complexes have been characterized by spectroscopic methods and their structures determined by X-ray crystallography. The 4-PDS ligands in 1 are coordinated to the metal centers through the nitrogen atoms to form 1-D zigzag-chains, and the distorted tetrahedral coordination geometry at each zinc center is completed by a pair of N-bonded thiocyanate ligands. Compound 2 has a 1-D channel-chain structure and each octahedral Fe(II) metal center is coordinated by four 4-PDS ligands and two trans N-bonded thiocyanate ligands. Weak SS interactions in complex 1 link the 1-D chains into 2-D molecular sheets. In complex 2, the channel chains are interlinked through SS interactions to form molecular sheets, which interpenetrate through the SS interactions to form 3-D structures with large cavities that are occupied by the water molecules. Compound 3 also has a 1-D channel-chain structure with each square-planar Co(II) metal center coordinated by four 4-PDS ligands. Multiple C–HCl hydrogen bonds and SO interactions in 3 link the 1-D chains into 2-D structures.     

Crystal structure and luminescence property of ternary terbium p-aminobenzoic acid complexes with different second ligands

Ternary terbium complexes with p-aminobenzoic acid (HL), [TbL₃(DMSO)(H₂O)]₂ (1), [TbL₃(DMF)(H₂O)]₂ (2) and [TbL₃(Bpy)(H₂O)]₂·2H₂O (3) (DMSO=dimethyl sulfoxide, DMF=N, N- dimethylformamide, Bpy=2, 2′- bipyridyl) have been synthesized, and their crystal structures determined. The luminescence properties of these complexes, including both the emission quantum yield and the fluorescence lifetime, have been investigated. The effect of a second ligand on the crystal structure and luminescence property of the ternary terbium p-aminobenzoic acid complexes, and the relationship between luminescence properties and crystal structure, including coordination mode of the L⁻ ligand and the characteristics of a second ligand, are discussed.     

Molecular, supramolecular structure and catalytic activity of transition metal complexes of phenoxy acetic acid derivatives

Six mononuclear complexes [M(L₁)₂(H₂O)₄] (M = Co(II), 1a and M = Mn(II), 1b), [Cu(L₁)₂(H₂O)₂] (1c), [Cu(L₁)₂(H₂O)(Py)₂] (1d), [Cu(L₃)(H₂O)Cl] · H₂O (3a) and [Co(Sal)(H₂O)(Py)₃] · 2ClO₄ · H₂O (3b) of phenoxyacetic acid derivatives and Schiff base were determined by single crystal X-ray diffraction. The Co(II) (1a) and Mn(II) (1b) complexes are isomorphous. X-ray crystal structural analyses reveal that these coordination complexes form polymeric structure via formation of different types of hydrogen bonding and π-stacking interactions in solid. Thermal analysis along with the powder X-ray diffraction data of these complexes shows the importance of the coordinated and/or crystal water molecules in stabilizing the MOF structure. Complexes 1a, 1c, 3a show marginal catalytic activity in the oxidation of olefins to epoxides in the presence of i-butyraldehyde and molecular oxygen.     

Manganese(II) complexes of 3,6,9-trioxaundecanedioic acid (3,6,9-tddaH2): X-ray crystal structures of [Mn(3,6,9-tdda) (H2O)2]·2H2O and {[Mn(3,6,9-tdda)(phen)2·3H2O]·EtOH}n

3,6,9-trioxaundecanedioic acid (3,6,9-tddaH₂) reacts with Mn(CH₃CO₂)₂·4H₂O in ethanol to give [Mn(3,6,9-tdda)]·H₂O (1). Recrystallization of 1 from methanol gives crystals of [Mn(3,6,9-tdda) (H₂O)₂]·2H₂O (2). Complex 1 reacts with an ethanolic solution of 1,10-phenanthroline (phen) to give {[Mn(3,6,9-tdda)(phen)₂]·3H₂O·EtOH}_n (3). All of the complexes are extremely water soluble. Complexes 2 and 3 were structurally characterised. The manganese(II) ion in 2 is seven coordinate, with an approximately pentagonal bipyramidal O₇ coordination sphere. The axial donors are water molecules and the pentagonal plane is occupied by the diacid, acting as a pentadentate ligand through the three ethereal oxygens and one oxygen atom from each of the carboxylate functions. In complex 3 the manganese(II) ion is six-coordinate, being bound to two bidentate phenanthroline ligands and to the carboxylate oxygen atoms from two symmetry related diacids which are coordinated in a cis fashion. The structure consists of polymeric chains, with diacid ligands bridging the manganese ions. There is π-π stacking of pairs of phenanthroline ligands on adjacent chains, running along both the z and y directions.     

Synthesis, structure and properties of delocalized transition metal chelates: Diazoketiminato chelates of Co(III) and Pt(II)

The reactions of HL 1 [where HL is 1N-(2-pyridyl-2-methyl)-2-arylazoaniline and is formulated as ArN = NC₆H₄N(H)(CH₂C₅H₄N); Ar = C₆H₅ (for HL¹) or p-MeC₆H₄ (for HL²) or p-ClC₆H₄ (for HL³)] with K₂PtCl₄ and Co(ClO₄)₃ · 6H₂O afforded the (L)PtCl and [(L)₂Co]ClO₄ complexes, respectively. The HL ligands bind the platinum(II) and cobalt(III) centres in a tridentate (N,N,N) fashion, forming new diazoketiminato chelates upon dissociating the amino proton. The X-ray structures of (L³)PtCl and [(L³)₂Co]ClO₄ were determined. Redox properties of the new complexes have been examined.     

Ion size dominated 1D and 2D Salen lanthanide coordination complexes and their luminescence

Lewis acid/base addition between Ln(NO₃)₃ · 6H₂O (Ln = Pr, Nd, Sm, Eu, Tb and Lu) and H₂salen [H₂salen = N,N′-ethylenebis(salicylideneimine)] gives rise to an array of coordination polymeric structures. Crystal structural analysis reveals that Salen effectively functions as a bridging ligand in these compounds. The size of the lanthanide ions controls the structures of these Salen lanthanide complexes. Two representative structures with one dimensional and two dimensional topologies, viz. [Pr(H₂salen)(NO₃)₃(CH₃OH)₂]_n (1) and [Ln(H₂salen)_1.5(NO₃)₃]_n [Ln = Pr (2), Nd (3), Sm (4), Eu (5), Tb (6) and Lu (7)] are reported. Luminescent spectra of complexes 4 and 5 exhibit characteristic metal-centered emission lines. However, the characteristic luminescence of the terbium(III) ion is not observed either in solution or in the solid state of complex 6.     

Thermal decomposition study on mixed ligand thymine complexes of divalent nickel(II) with dianions of some dicarboxylic acids

Thermal decomposition of mixed ligand thymine (2,4-dihydroxy-5-methylpyrimidine) complexes of divalent Ni(II) with aspartate, glutamate and ADA (N-2-acetamido)iminodiacetate dianions was monitored by TG, DTG and DTA analysis in static atmosphere of air. The decomposition course and steps of complexes [Ni(C₅H₆N₂O₂)(C₄H₅NO₄)²⁻(H₂O)₂]·H₂O, [Ni(C₅H₆N₂O₂)(C₅H₇NO₄)²⁻(H₂O)₂]·H₂O and [Ni(C₅H₆N₂O₂)(C₆H₈N₂O₅)²⁻(H₂O)₂]·1.5H₂O were analyzed. The final decomposition products are found to be the corresponding metal oxides. The kinetic parameters namely, activation energy (E*), enthalpy (ΔH*), entropy (ΔS*) and free energy change of decomposition (ΔG*) are calculated from the TG curves using Coats–Redfern and Horowitz–Metzger equations. The stability order found for these complexes follows the trend aspartate > ADA > glutamate.     

Three interpenetrated frameworks constructed by long flexible N,N′-bipyridyl and dicarboxylate ligands

Three interpenetrated polymeric networks, {[Co(bpp)(OH-BDC)] · H₂O}_n (1) [Ni(bpp)_1.5(H₂O)(OH-BDC)]_n (2) and {[Cd(bpp)(H₂O)(OH-BDC)] · 2H₂O}_n (3), have been prepared by hydrothermal reactions of 1,3-bis(4-pyridyl)propane (bpp), 5-hydroxyisophthalic acid (OH-H₂BDC), with Co(NO₃)₂ · 6H₂O, Ni(NO₃)₂ · 6H₂O and Cd(NO₃)₂ · 4H₂O, respectively. Single-crystal X-ray diffraction analyses reveal that the three compounds all exhibit interpenetrated but entirely different structures. Compound 1 is a fourfold interpenetrated adamantanoid structure with water molecules as space fillers, in which bpp adopts a TG conformation (T = trans, G = gauche). Compound 2 is an interdigitated structure from the interpenetrated long arms of one-dimensional molecular ladders, while bpp in 2 adopts both TT and TG conformations. Compound 3 is a twofold interpenetrated three-dimensional network from a one-dimensional metal-carboxylate chain bridged by TG conformational bpp. The hydrogen bonding interactions in 1–3 further stabilize the whole structural frameworks and play critical roles in their constructions.     

Synthesis, reaction and structure of a series of chromium(III) complexes containing oxalate ligand

A series of chromium(III) complexes [Cr(bipy)(HC₂O₄)₂]Cl·3H₂O (1), [Cr(phen)(HC₂O₄)₂]Cl·3H₂O (2), [Cr(phen)₂(C₂O₄)]ClO₄ (3), [Cr₂(bipy)₄(C₂O₄)](SO₄)·(bipy)_0.5·H₂O (4) and [Mn(phen)₂(H₂O)₂]₂[Cr(phen)(C₂O₄)₂]₃ClO₄·14H₂O (5) were synthesized (bipy=4,4′-bipyridine, phen=1,10-phenanthroline), while the crystal structures of 1 and 3–5 have been determined by X-ray analysis. 1 and 3 are mononuclear complexes, 4 contains binuclear chromium(III) ions and 5 is a 3D supromolecule formed by complicated hydrogen bonding. 1–3 are potential molecular bricks of chromium(III) building blocks for synthesis heterometallic complexes. When we use these molecular bricks as ligands to react with other metal salts, unexpected complexes 4 and 5 are isolated in water solution. The synthesis conditions and reaction results are also discussed.     

Hydrothermal synthesis, crystal structure and characterization of [Zn(H2O)4]2 [H2As6V15O42(H2O)]·2H2O

The compound [Zn(H₂O)₄]₂[H₂As₆V₁₅O₄₂(H₂O)]·2H₂O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) Å, c=33.970(7) Å, γ=120°, V=4278.8(12) Å³, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H₂As₆V₁₅O₄₂(H₂O)]⁴⁻ anions and [Zn(H₂O)₄]²⁺ cations linked through hydrogen bonds into a network. The [H₂As₆V₁₅O₄₂(H₂O)]⁶⁻ cluster consists of 15 VO₅ square pyramids linked by three As₂O₅ handle-like units.     

Synthesis, spectral properties, crystal structures and antimicrobial effects of copper(II) pyridinecarboxylate adducts with chelating ligands

The reaction of an ethanolic solution of copper(II) pyridinecarboxylates CuX₂·nH₂O (where X is nicotinate (nic) (n=0) or isonicotinate (isonic) (n=4)) with ethylenediamine (en) in a molar ratio of 1:2 lead to the isolation of solid tetragonally distorted octahedral complexes of the type [Cu(en)₂(H₂O)₂]X₂·nH₂O (n=1 for nic; n=0 for isonic). The analogous reaction of CuX₂·nH₂O with diethylenetriamine (dien) in a molar ratio of 1:1 leads to the formation of square-pyramidal pentacoordinated complexes of the type [CuX(dien)(H₂O)]X. On the other hand, the reaction of equimolar quantities of copper(II) nitrate and dien with nicotinate anions (equimolar quantities of pyridinecarboxylic acid and NaOH) in ethanolic solutions gives a solid monomeric complex [Cu(nic)(NO₃)dien)(H₂O)]·H₂O in which the coordination polyhedron around the Cu(II) atom is a (4+1+1) distorted tetragonal bipyramid. Based on the molecular structure the electronic and IR spectra are discussed. Moreover, the results of the quantitative determination of antimicrobial activity of the isonic complexes [Cu(isonic)₂(H₂O)₄], [Cu(en)₂(H₂O)₂](isonic)₂, [Cu(isonic)(dien)(H₂O)](isonic), as well as isonicotinic acid, ethylenediamine and diethylenetriamine alone are discussed.     

Second-sphere coordination in the complex [Mn(H2O)6]2[thiacalix[4]arene tetrasulfonate]

The title calixarene, dimanganese thiacalix[4]arene tetrasulfonate, was prepared and its crystal structure was determined. [Mn(H₂O)₆]₂[thiacalix[4]arene tetrasulfonate]·0.5H₂O crystallizes in the monoclinic system, P2(1)/m space group, with a=13.014 (6), b=14.146 (9), c=13.184 (7) Å, β=113.307 (10)°, V=2229 (2) Å³ and Dc=1.710 gcm⁻³, Z=2. The title calixarene exists in the solid state as bilayer structure. The hydrophobic organic layer consists of thiacalix[4]arene tetrasulfonate in an up-down fashion, whereas, the hydrophilic inorganic layer consists of hexaaquamanganese (II) which is linked to the former through a second-sphere coordination.     

Structural diversity of lanthanide–amino acid complexes under near physiological pH conditions and their recognition of single-stranded DNA

We reported here four structures of lanthanide–amino acid complexes obtained under near physiological pH conditions and their individual formula can be described as [Tb₂(dl-Cys)₄(H₂O)₈]Cl₂ (1), [Eu₄(μ₃-OH)₄(l-Asp)₂(l-HAsp)₃(H₂O)₇] Cl · 11.5H₂O (2), [Eu₈(l-HVal)₁₆(H₂O)₃₂]Cl₂₄ · 12.5H₂O (3), and [Tb₂(dl-HVal)₄(H₂O)₈]Cl₆ · 2H₂O (4). These complexes showed diverse structures and have shown potential application in DNA detection. We studied the interactions of the complexes with five single-stranded DNA and found different fluorescence enhancement, binding affinity and binding stoichiometry when the complexes are bound to DNA.     

Hydrogenmaleato bridged supramolecular double chains via π–π stacking interactions: syntheses, crystal structures and magnetic properties of ∞[Cu(phen)X(HL)2/2] with X=Cl (1), NO3 (2) and H2L=maleic acid

Two novel hydrogen maleato (HL) bridged Cu(II) complexes _∞¹[Cu(phen)Cl(HL)_2/2] 1 and _∞¹[Cu(phen)(NO₃)(HL)_2/2] 2 were obtained from reactions of 1,10-phenanthroline, maleic acid with CuCl₂·2H₂O and Cu(NO₃)₂·3H₂O, respectively, in CH₃OH/H₂O (1:1 v/v) at pH=2.0 and the crystal structures were determined by single crystal X-ray diffraction methods. Both complexes crystallize isostructurally in the monoclinic space group P2₁/n with cell dimensions: 1 a=8.639(2) Å, b=15.614(3) Å, c=11.326(2) Å, β=94.67(3)°, Z=4, D_calc=1.720 g/cm³ and 2 a=8.544(1) Å, b=15.517(2) Å, c=12.160(1) Å, β=90.84(8)°, Z=4, D_calc=1.734 g/cm³. In both complexes, the square pyramidally coordinated Cu atoms are bridged by hydrogen maleato ligands into 1D chains with the coordinating phen ligands parallel on one side. Interdigitation of the chelating phen ligands of two neighbouring chains via π–π stacking interactions forms supramolecular double chains, which are then arranged in the crystal structures according to pseudo 1D close packing patterns. Both complexes exhibit similar paramagnetic behavior obeying Curie–Weiss laws χ_m(T−θ)=0.414 cm³ mol⁻¹ K with the Weiss constants θ=−1.45, −1.0 K for 1 and 2, respectively.     

Large heteropolymetalate complexes formed from lanthanide (Y, Ce, Pr, Nd, Sm, Eu, Gd), nickel cations and cryptate [As4W40O140]: synthesis and structure characterization

A new family of heteropolytungstate complexes (NH₄)₂₁[Ln(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀]·xH₂O(Ln=Y, Ce, Pr, Nd, Sm, Eu, Gd) were prepared by the reaction of Na₂₇[NaAs₄W₄₀O₁₄₀]·60H₂O with NiCl₂·6H₂O and Ln(NO₃)₃·xH₂O at pH≈4.5. The crystal structures of (NH₄)₂₁[Gd(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀]·51H₂O was determined by X-ray diffraction analysis and element analysis. The compound crystallizes in the monoclinic space group P2₁/n with a=19.754(3), b=24.298(4), c=39.350(6) Å, β=100.612(3)°, V=18564(5) ų, Z=2, R1(wR₂)=0.0544(0.0691). The central site S1 and two opposite sites S2 of the big cyclic ligand [As₄W₄₀O₁₄₀]²⁸⁻ are occupied by one Ln³⁺and two Ni²⁺, respectively, each site supply four O_d coordinating to metal ion, another one water molecule and other five water molecules coordinate, respectively, to Ni²⁺and Ln³⁺. Polyanion [Ln(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀]²¹⁻ has C_2v symmetry. IR and UV–vis spectra of [NaAs₄W₄₀O₁₄₀]²⁷⁻ of the title compounds are discussed.     

Four Coordination Polymers Assembled with a New Biscarboxyl-functionalized Schiff Base Ligand

Based on a new biscarboxyl-functionalized Schiff base ligand 1,2-cyclohexanediamino-N,N'-bis[3-methoxyl-5-(p-carboxyl-phenylazo)] salicylidene(H₄L), four polymers,[(CH₃)₂NH₂]₂·[Mn₃(L)₂(H₂O)₄]·2DMF(CP1),[Fe₂(L)(H₂O)(DMF)](CP2),[(CH₃)₂NH₂]·[Cu(HL)]·H₂O(CP3) and[Ni₂(L)(teta)]·2DMF·H₂O(CP4), have been synthesized(teta=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). In CP1, both of the internal[N₂O₂] pocket and the external carboxylate groups of L^4- anion are ligated by Mn²⁺ ions, and the structure displays a layer. In CP2, the Fe²⁺ cations are linked by L^4- anions to form a binuclear double chain. CP3 displays a[Cu₂(HL)₂] dimer. In CP4, the Ni²⁺ ions are connected by L^4- anions to form a chain. The structures are further linked by hydrogen bonds to form 2D or 3D supramolecular architectures, respectively. CP1 exhibits adsorption ability to three organic dyes.     

Synthesis and structural characterization of mixed ligand η-2-hydroxyacetophenone complexes of cobalt(III)

A tridentate Schiff base ligand [(CH₃)₂NCH₂CH₂N=C(CH₃)C₆H₄OH)] (LH) has been synthesized from 2-hydroxyacetophenone and 2-dimethylaminoethylamine. This ligand forms the neutral complexes [Co(L)(N₃){o-(CH₃C=O)C₆H₄O}] (1) and [Co(L)(SCN){o-(CH₃C=O)C₆H₄O}]·1/2H₂O (2) in presence of equivalent amount of Co(II) acetate, and sodium azide for 1 and sodium thiocyanate for 2. The complexes have been characterized by spectroscopic and crystallographic methods. The coordination geometry around Co(III) in both the complexes is distorted octahedral with one tridentate ligand L, one bidentate 2-hydroxyacetophenone and one monodentate azide for 1 and thiocyanate for 2. The azide and thiocyanate ligands in the two complexes occupy different positions relative to the coordination sites of L.     

Supramolecular formation by aromatic ring stacking and hydrogen bonding in lanthanide(III) complexes with amino acids and 1,10-phenanthroline

[Eu(ABA)(phen)₂(H₂O)₃](ClO₄)₃·3phen·4.5H₂O (1) and [Eu(Val)(phen)₂(H₂O)₃](ClO₄)₃·3phen·2H₂O (2) are two new europium complexes with amino acids and 1,10-phenanthroline (phen=1,10-phenanthroline, ABA=-amino butyl acid, Val= -valine). Their crystal structures were measured by X-ray crystallography. Europium atoms in both complexes are nine-coordinated with bidentate 1,10-phenanthroline and carboxylate anion of amino acids, and water molecules. In the solid state, 1 and 2 have a structure involving aromatic stacking of the coordinated and non-coordinated 1,10-phenanthroline and the oxygen atoms of non-coordinated perchlorate anions being H-bond acceptors connect [Eu(ABA)(phen)₂(H₂O)₃]³⁺·3phen·4.5H₂O or [Eu(Val)(phen)₂(H₂O)₃]³⁺·3phen·2H₂O in their structures. In their interactions, several C–HO bonds play an important role. Owing to their different amino acid ligands and the number of lattice water molecules, there is some difference in their hydrogen bond patterns in 1 and 2. The side chain of -valine is involved in the formation of C–HO bonds. Hydrogen bond and π–π interactions determine the supramolecular formation of three-dimensional net works of both complexes.     

Complexes of ruthenium(II) and -(III) with dimethylsulphoxide—III. Bis-iodo-tetrakis- dimethylsulphoxide ruthenium(II) and some other iodo complexes of ruthenium(II)

The ruthenium(II) complex [RuI₂(Me₂SO)₄] was synthesized and characterized. The Me₂SO ligands are all S-bonded. Reactions of RuI₂(Me₂SO)₄ with ligands containing P, N and S donor atoms have been carried out and the complexes obtained were characterized using different physical methods. [RuI₂L₄] (L= CH₃CN, Me₂SO and py), [RuI₂(CH₃CN)₂(PPh₃)₂] and [RuI₂(CS)(PPh₃)₃] have been synthesized using RuI₃ as the source material and characterized as above.