Synthesis and Structures of Three Erbium(Ⅲ) Dicarboxylate Coordination Polymers

Three polymeric erbium(Ⅲ) complexes [Er(oba)(Hoba)(H 2O) 2]H 2O (A),[Er 2(oba) 3(H 2O) 4] (B), [Er 2(oba) 3(2,2′ bpy) 2] (C) (H 2oba=4,4′ oxybis(benzoic acid), 2,2′ bpy = 2,2′ bipyridine) were hydrothermally synthesized by altering the metal/carboxylate ratios or in the presence of an additional chelate 2,2′ bpy ligand, and characterized by single crystal X ray diffraction. The results show that different metal/carboxylate ratios can influence the polymeric structures and the presence of 2,2′ bpy ligand alters the topology of the framework from two dimensional to three dimensional.

Syntheses and Crystal Structure of Erbium(Ⅲ) Coordination Polymers with Two Flexible Double Betaine Ligands

Two new polymeric erbium(Ⅲ) complexes of two flexible double betaine ligands have been synthesized and characterized by X-ray analysis. In {[Er(L1)(H2O)4)Cl3 H2O}n (1) (L1 = 4, 4’ -trimethylenedipyridinio-N, N’-diacetate ), the erbium(Ⅲ) ions form a two-dimensional metal carboxylate layer in which each pair of Er(Ⅲ) atoms is bridged by two syn-anti μ-carboxylato-o,o’ groups, Adjacent layers arecross-linked through hydrogen bonds among aqua ligands, lattice water molecules andchloride ions to form a three-dimensional network. Complex l, C17 H28 N2 O9 ErC13 (Mr =676.0) is monoclinic, space group C2, with a= 27. 408(4), b= 9. 645 (3), c= 9. 423(2) A, p=1loo. 85(1)’, V=2446. 2(9) A’, Z=4, D=l. 836 g/cm’, F(OOO) =1332, μ(MoKa) = 38.06 cm-1, R=0. 048 for 2451 reflections with I>2σ(I). { [Er(L2 ) (H2O)4]Cl3. 5H2O}. (2) (L2=1, 3-bis (pyridinio-4-carboxylato) propane) comprises lanthanide carboxylate chains built from centrosymmetric dimeric units crosslinked by a pair of L2 ligands, discrete anions and lattice water molecules. In the dimeric unit of complex 2, each pair of metal ions is bridged by four syn-syn μ-carboxylatoO, O’ groups that are oriented nearly perpendicular to each other about the metal-metalaxis. The metal carboxylate chains of complex 2 are further cross-linked by hydrogenbonds to form a three-dimensional network. Complex 2, C15 H32 N2O13 ErCl3 (Mr=722.0) belongs to the monoclinic space group C2/m with a=16. 564 (3), b=15. 839(3), c=11. 792(4) , β=122. 27(1)°, V=2616(1), Z=4, Dc=1.833 g/cm3,F(000) =1436, μ (MoKa) = 35. 75 cm-1, R =0.043 for 2436 observed reflectionswithI>2σ(I).

Ionothermal Synthesis,Structure and Luminescent Properties of a New 2-D Bismuth(Ⅲ) Coordination Polymer with(6,5)-Connected Topological Sheet

A new 2-D Bi（3＋） coordination polymer {Bi4（μ3-O）2（μ4-O）2（C7H3NO4）2}n（1,C7H3NO4 = pyridine-2,6-dicarboxylate） containing（6,5）-connected topological sheet with the Schl？fli symbol of（4~4·6~3·8~4·12~4）（4~5·6~4·8） has been synthesized by an ionothermal method using the ionic liquid 1-ethyl-3-methylimidazolium bromide（[Emim]Br） as solvent,and characterized by C,H and N elemental analysis,energy-dispersive X-ray spectroscopy（EDS）,infrared spectrum（IR spectrum） and single-crystal X-ray diffraction.The results indicate that 1 belongs to the monoclinic system,space group P21/n with a = 13.766（7）,b = 4.142（2）,c = 16.439（8） ？,β = 99.099（9）°,Z = 2,V = 925.6（8） ？~3,Dc = 4.414 g·cm^（-3）,F（000） = 1064,μ = 37.985 mm-1,the final R = 0.0326,wR = 0.0727 and S = 1.022.The molecular structural units [Bi4（μ3-O）2（μ4-O）2（C7H3NO4）2] are connected to each other via bridging O atoms,extending into an interesting 2-D layered structure.These resulting layers are further assembled by weak C-H…O hydrogen bonds into a 3-D supramolecular architecture.Moreover,its thermal stability and the luminescent properties have been also studied.

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） nm, 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 LaIn 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.

A Two-dimensional Gadolinium(Ⅲ) Coordination Polymer with 5-Hydroxynicotinatic Acid and Oxalate Ligands and Magnetic Property

A new coordination polymer, [Gd（III）（3-H-5-hydroxynicotinato）（ox）l.s（H20）2]n, has been synthesized by a hydrothermal reaction of gadolinium nitrate with 5-hydroxynicotinic acid and ammonium oxalate, and its structure has been determined by X-ray crystallography with the following data： triclinic space group PI, CgHgNOIlGd, Mr = 464.42, a = 7.5545（11）, b = 8.1094（12）, c = 10.6947（16） A, a= 103.493（2）, β = 98.385（2）, y= 92.117（2）°, Z= 2, V= 628.5706） A3, F（000） = 444, Dc = 2.454 g.cm^-3,/2 = 5.341 mm^-1, the final R = 0.0188 and wR = 0.0392 for 2634 observed reflections （I 〉 2σ（I））. In the asymmetric unit of the compound, each Gdm ion is bonded to nine oxygen atoms from 3-H-5-hydroxynicotinato and oxalate groups and terminal-coordinated water molecules, respectively, resembling a highly distorted three-capped trigonal geometry. Adjacent GdO9 coordination polyhedra are bridged by three identical independent oxalate groups in a side-by-side manner forming brickwall-like 2D grids, and then further linked through intermolecular hydrogen bonds generating a 3D supramolecular network. Magnetic analysis of the compound shows that weak antiferromagnetic coupling exists among the adjacent Gdm ions.

Synthesis, Characterization and X-Ray Structure of a Ba(II)/Ag(I)/Cr(III)-Oxalate Salt with Water-Filled Nanochannels

A novel mixed barium(II)/silver(I)/chromium(III) oxalate salt, Ba0.5Ag2[Cr(C2O4)3]·5H2O (1), with open architecture has been synthesized in water and characterized by elemental analysis, vibrational and electronic spectra, and single crystal X-ray structure determination. Compound 1 crystallizes in a monoclinic space group C2/c, with unit cell parameters a = 18.179(3), b = 14.743(2), c = 12.278(2)Å, β = 113.821(3), V = 3010.34(90) Å3, Z = 8. The structure is characterized by a network of anionic [Cr(C2O4)3]3- units connected through the O atoms of the oxalates to Ba2+ and Ag+ sites, forming a three-dimensional coordination polymer with one-dimensional isolated nanochannels parallel to the c axis, and encapsulating hydrogen-bonded guest water molecules. The bulk structure is consolidated by O–H···O bridgings within the nanochannels and by coulombic interactions.

Synthesis of an Indium-iminodiacetate Two-dimensional Layer Network with Rhombus Grids

The title compound, [InCl（C4H5NO4）]n, has been synthesized via the hydrothermal method and characterized by IR, elemental analysis, UV-Vis-Nir spectra and single-crystal X-ray diffraction analysis. Single-crystal X-ray analyses show that it is a carboxylate-bridged two-dimensional layer network indium（III） polymer, catena-poly[[chloroindium（III）]-μ-（iminodiacetate к4N,O,O＇：O＇＇：O＇＇＇]. The crystal is of orthorhombic system, space group Pnma with a = 13.5970（13）, b = 8.7671（10）, c = 6.0427（5）, C4H5ClInNO4, Mr = 281.36, V = 720.33（12）3, Z = 4, Dc = 2.594 g/cm3, F（000） = 536, μ = 3.613 mm-1, R = 0.0245 and wR = 0.0570. The In（III） ion exhibits an approximately octahedral InClNO4 coordination environment, with the two O donor atoms of iminodiacetate and two O atoms belonging to the carboxylate group of two adjacent iminodiacetates occupying the basal positions, and the chlorine ion and one nitrogen atom of iminodiacetate in the apical sites. Carboxylate groups are mutually cis oriented, and each syn-anti carboxylate group bridges two indium（III） ions via two different basal positions, resulting in the formation of a 2-D network with rhombus （4, 4） grids. Each rhombus grid unit is formed from four indium atoms and four iminodiacetate units with the diagonal lengths of 8.767（1） and 6.043（1）.

一个三维发光铕配位聚合物的晶体结构及分子识别性能研究

使有机配体1,4-苯二甲酸(H_2DCB)与硝酸铕在DMF(N,N-二甲基甲酰胺)和水的混合溶剂中,通过溶剂热反应,制备出结构新颖的三维发光配位聚合物[Eu(DCB)1.5DMF]n(1)。对其分子结构通过元素分析、红外光谱、PXRD以及单晶X-ray进行了表征。研究了1在空气气氛下的热分解特点以及固态荧光光谱,进而测试了其阳离子以及小分子识别性能,发现其对甲苯和四氢呋喃具有一定的识别作用。

香豆素-3-羧酸铒(Ⅲ)一维配位聚合物[Er(CCA)_3(H_2O)_2]_n·2nH_2O的溶剂热法合成、晶体结构及与牛血清白蛋白(BSA)的相互作用

利用溶剂热法合成了一维配位聚合物[Er(CCA)3(H2O)2]n·2nH2O(HCCA=香豆素-3-羧酸),通过元素分析和IR对配合物进行了表征,用X-射线单晶衍射技术测定了其晶体结构.标题配合物晶体属于单斜晶系,P21/c空间群:a=0.6310(1)nm,b=1.4165(2)nm,c=3.1731(3)nm;β=91.861(2)°,V=2.8346(7)nm3,Dc=1.890 g·cm-3,Z=4,F(000)=1596,残差因子R1=0.0525,wR2=0.0930[I>2σ(I)],S=1.290.配合物的金属中心与来自配体(CCA)和配位水分子的8个氧原子进行配位,形成了一个畸变的十二面体,两个相邻的铒(Ⅲ)离子通过一个羧基桥连成为一维聚合物.用荧光光谱法研究了不同温度下配合物与牛血清白蛋白(BSA)的相互作用,结果表明,配合物对BSA的荧光猝灭属于静态猝灭,计算了不同温度下配合物与BSA间的结合常数(Ka),结合位点(n)及相关热力学参数(ΔH>0,ΔS>0),二者主要靠疏水作用力结合.依据Fster’s非辐射能量转移理论,求得给体(BSA)与受体(配合物)间的距离r=2.85 nm,说明配合物与BSA之间发生了非辐射能量转移.