邻苯二甲酸根桥联镍配位聚合物的合成与晶体结构

合成了邻苯二甲酸根桥联镍配位聚合物{ [ Ni(phth) (phen) (H2O) ]·H2O}n(phth:邻苯二甲酸根二价阴离子;phen: 1, 10-邻菲咯啉),并得到了它的单晶.用X射线单晶衍射法测定了配合物的晶体结构.     

3-羧基水杨醛·邻菲咯啉合铜(Ⅱ)配合物的合成与晶体结构

合成了铜(Ⅱ)与3-羧基水杨醛和邻菲咯啉的配合物[Cu(sal)(phen)].4 H2O(sal为3-羧基水杨醛负二价离子,phen为邻菲咯啉),采用单晶X射线衍射法测定了配合物的晶体结构.结果表明,合成的晶体属于三斜晶系p墿空间群;晶体参数a=0.673 02(10)nm,b=1.102 11(19)nm,c=1.488 3(2)nm,α=109.275(2)°,β=91.991(2)°,γ=103.514(2)°;分子中Cu(Ⅱ)离子处于平面四方场配位环境中.     

过渡金属离子与3-氟邻苯二甲酸和1,10-邻菲啰啉配合物的合成、结构及性质

过渡金属离子与3-氟邻苯二甲酸(H2Fpht)、1,10-邻菲啰啉(phen)通过水热反应得到了5个配合物:[M(Fpht)(phen)(H2O)3]·H2O(M=Ni 1,Co 2),[Cu(Fpht)(phen)(H2O)]·H2O(3),[M(Fpht)(phen)(H2O)]·H2O(M=Zn 4,Cd 5)。通过X-射线单晶衍射分析、元素分析、红外分析、荧光分析以及差热-热重分析对配合物进行了表征。配合物1和2为单核分子,中心离子Ni(Ⅱ)和Co(Ⅱ)与3-氟邻苯二甲酸根的1个氧原子,1,10-邻菲啰啉的2个氮原子以及3个配位水分子的3个氧原子配位,形成六配位的扭曲八面体构型。配合物3为Z字形一维链状结构。中心Cu(Ⅱ)离子与2个3-氟邻苯二甲酸根的2个氧原子,1个1,10-邻菲啰啉的2个氮原子以及水分子的1个氧原子配位,形成四方锥构型。配合物4和5具有相似的一维螺旋结构,中心Zn(Ⅱ)和Cd(Ⅱ)离子与2个3-氟邻苯二甲酸根的3个氧原子、1,10-邻菲啰啉的2个氮原子以及水分子中的1个氧原子配位,形成扭曲的八面体构型。     

邻苯二甲酸根桥联Zn(Ⅱ)超分子配合物的合成、表征和晶体结构

用Zn(NO3 ) 2 ,phen(邻菲咯啉 )和phth(邻苯二甲酸 )混合反应得到了配位聚合物 {[Zn2 (phen) 2 (phth) 2 (H2 O) 2 ]·2H2 O}n.通过元素分析、红外光谱对配合物进行了表征 .用X射线单晶衍射仪测定了配合物的晶体结构 .配合物为单斜晶系 ,P2 ( 1) /n空间群 .晶胞参数a =0 964 3 ( 3 )nm ,b =0 8976( 3 )nm ,c =2 14 10 ( 7)nm ,β =90 776( 5 )° ,Z =4,V =1 85 3 1( 10 )nm3 ,Dc=1 5 98g/cm3 ,μ =1 3 67mm-1,F( 0 0 0 ) =912 ,R1=0 0 40 9,wR2 =0 0 818,锌原子为五配位 ,呈畸变三角双锥构型 ,通过邻苯二甲酸根的桥联作用形成了一维螺旋链状结构 ,相邻的螺旋链之间靠π π堆积形成二维网状超分子结构 .     

三维网状配位聚合物{[Cd2(phen)2(H2O)2(C6H5NO2)2]·(ClO4)}n的水热合成、晶体结构及荧光性质

以异烟酸和邻菲咯啉(phen)为原料,采用水热合成方法,合成了一个新的配位聚合物{[Cd2(phen)2(H2O)2(C6H5NO2)2]·(ClO4)}n,测定了其晶体结构.结果表明:该配合物晶体属单斜晶系,空间群P21/n.与中心镉(Ⅱ)离子配位的3个氧原子分别来自2个异烟酸根和1个水分子,3个氮原子分别来自1个异烟酸根和1个邻菲咯啉,形成六配位变形八面体结构.由于异烟酸的桥联作用及氢键作用,配合物堆积成三维网状结构;同时配合物通过异烟酸的羧基双齿桥联配位以及邻菲咯啉和水分子作为端基配位.形成了双核笼状结构,其Cd(Ⅱ)…Cd(Ⅱ)距离为0.8798 nm.此外,还研究了该聚合物的荧光性质.     

铜(Ⅱ)-N-(2-羟苄基)-DL-α-苯丙氨酸-2,2′-联吡啶(或1,10-邻菲咯啉)三元配合物的合成、晶体结构及抑菌活性

合成了铜"与N-(2-羟苄基)-DL-α-苯丙氨酸(H2sphe)和2,2′-联吡啶(2,2′-bipy)及1,10-邻菲咯啉(phen)的三元配合物[Cu(Hsphe)(phen)](ClO4)·3H2O(1)、[Cu(Hsphe)(2,2′-bipy)](ClO4)(2)、[Cu(Hsphe)(2,2′-bipy)](NO3)(3)。用X射线单晶衍射测定了配合物的晶体结构。3种配合物中Cu"离子配位数均为5,处于变形四方锥配位环境中。抑菌活性试验结果表明,3种配合物均对金黄色葡萄球菌、铜绿假单胞菌和枯草杆菌有一定的抑制作用。配合物1还对大肠杆菌、伤寒杆菌有较强的抑制作用,而配合物3对伤寒杆菌亦有一定的抑制作用。     

单核Zn(Ⅱ)/Ni(Ⅱ)含氮配体配合物的合成、晶体结构及性质

合成了2个新的配合物[Zn(BPP)2(H2O)4](2,6-NDS)·0.5H2O(1)和[Ni(phen)2(H2O)2](A-2,5-DSA)·3H2O(2)(2,6-NDS=2,6-萘二磺酸根,A-2,5-DSA=苯氨-2,5-二磺酸根,BPP=1,3-二(4-吡啶基)丙烷,phen=1,10-邻菲咯啉),用X-射线单晶衍射结构分析方法测定了配合物的晶体结构。配合物1是单核分子,Zn2+离子与2个1,3-二(4-吡啶基)丙烷的2个N原子及4个水分子配位,形成单核配位阳离子。相邻配位阳离子通过配位水分子与氮原子的氢键作用联接成一维双螺旋阳离子链。双螺旋阳离子链与未配位的2,6-萘二磺酸根阴离子通过氢键作用形成二维超分子网。配合物2是单核分子,Ni2+离子与2个1,10-邻菲咯啉分子中的4个N原子及2个水分子配位,形成单核配位阳离子。配位阳离子与游离的水分子及苯氨-2,5-二磺酸根阴离子通过氢键作用构筑成二维超分子网。     

6-甲基-2,3,5-吡啶三甲酸构筑的两个银配合物的合成、结构与性质

以6-甲基-2,3,5-吡啶三甲酸,菲咯啉为配体与AgNO3反应,合成出2种银配合物[Ag(H2mptc)(phen)]·2H2O(1)和[Ag(H2mptc)(phen)](2)(H3mptc=6-甲基-2,3,5-吡啶三甲酸,phen=菲咯啉),并对其进行了红外光谱分析,元素分析,热重分析,X-射线粉末衍射分析,荧光光谱分析及X-射线单晶衍射结构分析。配合物1中的Ag(Ⅰ)采取三配位的配位方式与配体H2mptc-及phen中的N原子结合,在2中,除了3个N原子配位外,邻位羧基的O原子也参与了配位。通过计算得知配合物2是热力学上更稳定的结构。固体荧光光谱表明,1和2在475 nm左右有最大吸收,相对配体有75 nm左右的红移,均可归属于配体到金属间的电荷转移。     

铜与苯甲酸和邻菲咯啉三元配合物的合成与晶体结构

合成了铜 (Ⅱ )与苯甲酸和邻菲咯啉三元配合物 [Cu(ba) 2 (phen) (H2 O) ] (ba :苯甲酸 ;phen :1,10 邻菲咯啉 ) ,得到了它的单晶。用X射线衍射法测定了配合物的晶体结构。晶体学数据如下 :C52 H4 0 Cu2 N4 O10 ,Mr=10 0 7.96 ,单斜 ,P2 1/n ,a =10 .45 5 (1) ,b =2 1.2 6 3(2 ) ,c =11.199(2 ) ;β =117.6 90 (10 )°,Z =2 ,V =2 2 0 4.5 (5 ) 3,F(0 0 0 ) =10 36 ,Dc=1.5 19Mg/m3,μ =1.0 33mm- 1。晶体分子配位中心Cu(Ⅱ )离子的配位数为 5 ,这五个配位原子形成一个畸变的四方锥结构 ,配合物分子因分子间氢键作用以二聚体形式存在。     

1，2-环己二羧酸及芳香含氮配体的双核镉、锰配合物的合成和晶体结构

用水热法合成了两种新的配合物[Cd2(e,e-trans-chdc)2(bipy)2(H2O)2].H2O(1)和[Mn2(e,a-cis-chdc)2(phen)2(H2O)2].2H2O(2)(chdc=1,2-环己二羧酸,bipy=2,2′-联吡啶和phen=1,10-邻菲咯啉),用X-射线单晶衍射分析确定了配合物的晶体结构。配合物1和2均为双核分子。配合物1中,2个镉髤离子由2个1,2-环己二羧酸根以e,e-trans配位方式桥联,每个镉髤离子与1个2,2′-联吡啶的2个氮原子、2个1,2-环己二羧酸根的4个氧原子及1个水分子中的氧原子配位,形成了单帽变形三棱柱构型。配合物2中,2个锰髤离子由2个1,2-环己二羧酸根以e,a-cis配位方式桥联,每个锰髤离子与1个1,10-邻菲咯啉的2个氮原子、2个1,2-环己二羧酸根的3个氧原子及1个水分子中的氧原子配位,形成了畸变的八面体构型。配合物1和2分子之间都存在π-π堆积和O-H…O、C-H…O弱作用,进而将双核分子连接成三维超分子网络结构。配合物的荧光均来自于配体的荧光。     

Synthesis,crystal structure,and luminescence of a quaternary binuclear europium complex [Eu2(phth)2(Hphth)2(phen)2(H2O)4]

A quaternary binuclear europium complex [Eu₂(phth)₂(Hphth)₂(phen)₂(H₂O)₄] (H₂phth?=?phthalic acid, phen?=?1,10-phenanthroline) has been synthesized. The structure was determined by X-ray crystallography which reveals that it is binuclear with each europium nine-coordinate. Intermolecular hydrogen bonds link the complex units to form a 3D supermolecular network. Its properties have been studied by means of luminescence spectrum and thermal analysis. Fluorescence spectra show that the complex exhibits strong red emission.     

Syntheses,Structures, and Properties of Five Coordination Polymers Involving Phthalic Acid

Five new coordination polymers Cu(phen)(H2O)(phth)·CH3OH(1), [Cu(2,2'-bipy)(H2O)](phth)·3.5H2O(2), Zn(phen)(phth)(H2O)·1.125H2O(3) and [M(4,4'-bipy)(H2O)2](phth)·2H2O[M=Zn(4), Mn(5)](H2phth=phthalic acid, bipy=bipyridine, phen=1,10-phenanthroline) have been synthesized from the amino acid derivatives(phthalyl-l- valine, H2L) and structurally characterized. H2L was hydrolyzed into phth2– group during the reaction, but the strucure feature was different from that of the complex directly synthesized from H2phth in the reported literature, revealing that H2L played an important role in composing the novel compounds. Compounds 1, 2 and 3 are all 1D chains, but the differences are that compound 1 is further hydrogen-bonded into 2D networks, and compound 2 is further extended into 3D supramolecular network through π-π stacking and hydrogen-bonding interactions. However, compound 3 is a 1D helix chain structure and further links into 2D networks through π-π stacking. Compounds 4 and 5 are isostructural and exhibit the same 2D layers, which are further connected by hydrogen-bonding interactions to form 3D supramolecular network. Antiferromagnetic superexchange was observed for compounds 1, 2 and 5.     

Synthesis and Crystal Structure of a Coordination Polymer {[Co(phth)(phen)(H2O)]·(C2H5OH)}n

The coordination polymer {[Co(phth)(phen)(H2O)]·(C2H5OH)}n (phth = phthalate, phen = 1,10-phenanthroline) with formula C22H20CoN2O6 (Mr = 467.33) was synthesized by the solvothermal method under low temperature, and its crystal structure was determined by singlecrystal X-ray diffraction. The complex belongs to monoclinic system, space group P21/n with a =12.7352(16), b = 8.8125(11), c = 18.677(2) (A), β = 102.633(2)°, V = 2045.3(4) (A)3, Z = 4, Dc =1.518 g/cm3,μ = 0.882 mm-1, F(000) = 964, S = 1.053, the final R = 0.0401 and wR = 0.0984 for 3135 observed reflections (I ＞ 2σ(I)). Single-crystal X-ray analysis revealed that the Co(Ⅱ) ion is six-coordinated. The cobalt complex forms a one-dimensional chain structure via phthalate bridging ligand. In the cobalt complex, a 3D network structure is formed by π-π stacking interaction of 1,10-phenanthroline as well as intermolecular hydrogen bonding interactions.     

Synthesis and Crystal Structure of a Coordination Polymer {[Co(phth)(phen)(H_2O)]·(C_2H_5OH)}_n

1 INTRODUCTION Metal-organic coordination polymer has particu- lar and special structure characters with some caves, holes and channels[1], and can be used in selected catalysis, molecular recognition, reversible exchan- ge of host-guest molecules (ions), super purity sepa- ration, biological conductor[2～5], etc. In the past ten years, polymers with bridging ligand have been widely investigated[6, 7]. The development of supra- molecular architectures of inorganic-organic hybrid molecules …     

系列Cu(Ⅱ/Ⅰ)配合物的制备及其表面光电压

采用水热法合成了{[Cu(phen)(H2O)(o-tpha)]·H2O}n(1), [Cu2Cl4(phen)2](2), [Cu4Cl4·(bipy)2](3)和[Cu2Cl2(phen)]n(4)(bipy=2,2'-bipyridyl, phen=1,10-phenanthroline, o-H2tpha=o-phthalic acid)4个铜配合物. X射线单晶衍射结果表明, 配合物1和4是具有一维无限结构的聚合物, 配合物2是双核Cu(Ⅱ) 配合物并由氢键连成超分子, 配合物3是四核Cu(Ⅰ) 簇合物. 常温下测定了4个配合物的表面光电压光谱(SPS)、场诱导表面光电压光谱(FISPS)、IR和UV-Vis-NIR光谱. SPS的测试结果显示, 4个化合物均在300~800 nm范围内存在光伏响应带, 但是它们呈现了不同的特性. 配合物1~3的表面光电压光谱呈现出正的表面光伏响应(SPV), 配合物4的SPS呈现出负的表面光伏响应. 4个配合物的表面光伏响应带的位置、数量以及强度均有明显不同.     

Synthesis, characterization, and luminescence properties of the ternary europium complex covalently bonded to mesoporous SBA-15

A novel mesoporous SBA-15 type of hybrid material (phen-SBA-15) covalently bonded with 1,10-phenanthroline (phen) ligand was synthesized by co-condensation of tetraethoxysilane (TEOS) and the chelate ligand 5-[N,N-bis-3-(triethoxysilyl)propyl]ureyl-1,10-phenanthroline (phen-Si) in the presence of Pluronic P123 surfactant as a template. The preservation of the chelate ligand structure during the hydrothermal synthesis and the surfactant extraction process was confirmed by Fourier transform infrared (FTIR) and (29)Si MAS NMR spectroscopies. SBA-15 consisting of the highly luminescent ternary complex Eu(TTA)(3)phen (TTA = 2-thenoyltrifluoroacetone) covalently bonded to a silica-based network, which was designated as Eu(TTA)(3)phen-SBA-15, was obtained by introducing the Eu(TTA)(3).2H(2)O complex into the hybrid materials via a ligand exchange reaction. XRD, TEM, and N(2) adsorption measurements were employed to characterize the mesostructure of Eu(TTA)(3)phen-SBA-15. For comparison, SBA-15 doped with Eu(TTA)(3).2H(2)O and Eu(TTA)(3)phen complexes and SBA-15 covalently bonded with a binary europium complex with phen ligand were also synthesized, and were named SBA-15/Eu(TTA)(3), SBA-15/Eu(TTA)(3)phen, and Eu-phen-SBA-15, respectively. The detailed luminescence studies on all the materials showed that, compared with the doping sample SBA-15/Eu(TTA)(3)phen and binary europium complex functionalized sample Eu-phen-SBA-15, the Eu(TTA)(3)phen-SBA-15 mesoporous hybrid material exhibited higher luminescence intensity and emission quantum efficiency. Thermogravimetric analysis on Eu(TTA)(3)phen-SBA-15 demonstrated that the thermal stability of the lanthanide complex was evidently improved as it was covalently bonded to the mesoporous SBA-15 matrix.     

Thermally stable luminescent composites fabricated by confining rare earth complexes in the two-dimensional gallery of titania nanosheets and their photophysical properties

Fluorescent composite materials of exfoliated titania nanosheets, Ti(0.91)O(2), and rare earth (RE) complexes, Eu(phen)(2)Cl(3).2H(2)O and Tb(phen)(2)Cl(3).2H(2)O (phen = 1,10-phenanthroline), were synthesized via flocculation between them. X-ray diffraction measurements and transmission electron microscopy observations confirmed a restacked lamellar structure for the composites, and elemental analysis revealed a high RE complex content of 15 wt %. The decomposition temperature of the complexes trapped in the composites was improved to 420 degrees C from 250 degrees C for the free form. The restacked composite composed of Ti(0.91)O(2) nanosheets and Eu(phen)(2) exhibited characteristic red emission from the complex, while the composite with Tb(phen)(2) gave featureless emission originated from the ligand. This phenomenon can be explained by a shift of triplet state level of the ligand after encapsulation in the host titania nanosheets. The quantum yield of europium complex in the composite was enhanced 1.6 times more than that of the pure complex.     

Analysis of weak interactions in the crystal packing of inorganic metalorganic hybrids based on Keggin polyoxometalates and dinuclear copper(II)-acetate complexes

Reaction of in situ generated copper-monosubstituted Keggin polyoxometalate (POM) and copper-phenanthroline complexes in potassium or sodium acetate buffers led to the formation of the potassium salt of [[SiW(11)O(39)Cu(H(2)O)][Cu(2)(phen)(2)(H(2)O)(ac)(2)]](4-) (1) and [[Si(2)W(22)Cu(2)O(78)(H(2)O)][u(2)(phen)(2)(H(2)O)(ac)(2)](2)](8-) (2, where phen = phenanthroline and ac = acetate) hybrid polyanions, respectively. Both compounds are the first discrete mono- and bimolecular transition-metal-substituted Keggin POMs that support a binuclear copper-acetate complex. Despite the different nature of the POMs, the crystal packing of the two compounds is closely related, being formed of hybrid parallel layers that give rise to an alternate sequence of inorganic and metalorganic regions. This packing type seems to be determined by the extensive network of weak intermolecular interactions established by the dicopper complexes, as a Hirshfeld surface analysis shows. Electron paramagnetic resonance studies indicate that both the supported [Cu(2)(ac)(2)(phen)(2)(H(2)O)](2+) complexes and the copper(II)-monosubstituted POMs are magnetically isolated.     

Synthesis and Structure of a Novel Macrocyclic Complex [Cd2(phen)4(phth)2]·4H2O

A novel complex [Cd2(phen)4(phth)2]·4H2O has been synthesized by the reaction of H2phth(phthalic acid) and phen(1,10-phenanthroline) with Cd(Ⅱ) in ethanol-water solution. X-ray crystal structure analysis shows it crystallizes in triclinic, space group P1 with a = 10.619(3), b =12.560(4), c = 12.651(4) A, α = 98.775(5), β = 109.035(5), γ = 113.576(5)°, C32H24CdN4O6, Mr=672.95, V= 1381.7(7) A3, Rint = 0.0358, Z= 2, Dc= 1.618 g/cm3, μ = 0.845 mm-1, -6 ≤h≤13, -15≤k ≤13, -15≤l≤14, F(000) = 680, S = 1.038, R = 0.0480 and wR = 0.0849 for 3992 observed reflections (I ＞ 2σ(Ⅰ)). Phth bridges Cd(Ⅱ) to form a macrocyclic compound, and a 2D supramolecular motif is formed through hydrogen bonds and π-π interaction.