芳香碘基辅助的配位超分子自组装--锌(Ⅱ)、镉(Ⅱ)与7-碘-8-羟基喹啉-5-磺酸配合物的合成和结构

合成了锌(Ⅱ)、镉(Ⅱ)与7-碘-8羟基喹啉-5-磺酸(IHQS)的两种单晶配合物[Zn(IHQS)(H2O)3]2·4H2O(1)和[Cd-(IHQS)(H2O)2]n·2nH2O(2),用X射线衍射法确定了结构.结果表明,1和2均由一对对映体配合物构成1中两个[Zn-(IHQS)(H2O)3]对映体通过磺酸基-锌(Ⅱ)八面体轴向互补配位形成中心对称双分子聚合体,该聚合体通过分子间磺酸基氧-配位水氢键形成独特的二维层状结构;2的两个[Cd(IHQS)(H2O)2]对映体通过镉(Ⅱ)-磺酸基-镉(Ⅱ)双向互补配位形成一维直线型聚合配位结构.芳香碘基呈现新颖的碘-芳环氢和碘-磺酸基氧等弱相互作用模式,并对上述结构的支撑稳定发挥重要的结构辅助作用.本文展示了芳香碘基、磺酸基和喹啉环三种弱相互作用基团在配位超分子自组装中的形状、空间匹配和协同促进模式.结晶学参数配合物1单斜晶系,C2/c空间群,a=2.2243(7)nm,b=1.0053(3)nm,c=1.3468(4)nm,β=102.267(5)°,V=2.9428(16)nm3和Z=4.配合物2三斜晶系,P1空间群,a=0.6949(2)nm,b=1.0183(3)nm,c=1.0989(3)nm,α=76.069(5)°,β=75.294(5)°,γ=84.747(5)°,V=0.7295(4)nm3和Z=2.     

[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O超分子化合物的晶体结构、荧光性质及热稳定性

在水-乙醇混合体系中,以2-羰基丙酸水杨酰腙(C10H10N2O4,简作H3L)、1,10-菲啰啉C12H8N2,简作phen)与Eu(NO3)3·4H2O反应,首次培养出黄色单晶[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O.该晶体属三斜晶系,P1空间群,晶胞参数a=1.378 6(12) nm,b=1.398 8(12) nm,c=1.759 7(16) nm,α=73.977(11)°,β=68.598(12)°,γ=71.224(12)°,V=29.42(4) nm3,Z=2,μ=2.208 mm-1,Dc=1.746 Mg/m3,F(000)=1 556,R=0.037 7,ωR=0.074 4,GOF=0.916.每个配合物晶体中均有两个相似的结构单元,每个结构单元中铕(Ⅲ)配位数为9,分别与两个2-羰基丙酸水杨酰腙和3个水分子配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和CN中的氮与Eu3+配位,形成两个共边的稳定的五元环,另3个配位原子则分别来自3个水分子中的氧原子,该结构单元在空间呈扭曲的单帽四方反棱柱,而在每两个铕的九配位单元周围还有一个游离的1,10-菲啰啉分子和4个水分子.IR,1H NMR及热分解结果佐证了配合物的组成.该配合物具有很好的荧光特性.     

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。     

Synthesis and Structure of a Novel Cobalt(Ⅱ)Complex with the Tertiary Carbinol Derivative of Di-4-pyridinylmethanone

The title complex [Co[(4-C5H4N)2C(OH)(NHC3H7)]2(NO3)2]∞ was obtained and characterized through elemental analysis, FT-IR and X-ray crystallography. The complex crystallizes in space group P3(2)21 with a=10.2480(11), b=10.2480(11), c=26.943(6), β=120.00°, [Co[(4-C5H4N)2C(OH)(NHC3H7)]2(NO3)2]∞, C28H34CoN8O8 , Mr=669.56, Z=3, V=2450.5(7)3 , Dc=1.361 g·cm-3 , μ=0.584 mm-1 , F(000)=1047, R=0.0498 and wR=0.1301. The Co(Ⅱ) center exhibits a N4O2-octahedral coordination geometry surrounded by a pair of nitrates at the axial positions and four pyridyl N atoms at the equatorial sites. An infinite double-bridged chain structure with μ2-bridging (4-C5H4N)2C(OH)(NHC3H7) ligands is formed, which is the in situ product of metal-promoted nucleophilic addition reaction of propan-1-amine with di-4-pyridinylmethanone ((4-C5H4N)2CO) in the presence of Co(NO3)2·6H2O. It is the first tertiary carbinol metal complex derived from di-4-pyridinylmethanone so far, and also the rare example of tertiary carbinol derivative of dipyridylmethanone family. The nucleophilic reaction at the carbonyl of dipyridylmethanone in the presence of metal salt will be discussed.     

镝(III)与酰腙及1,10菲啰啉多元配合物的晶体结构及荧光性质

在水乙醇混合体系中 ,首次得到 2 羰基丙酸水杨酰腙 (C10 H10 N2 O4) ,1,10 菲啉 (C12 H8N2 ,简写作phen)与Dy(NO3 ) 3 ·3H2 O的配合物 [Dy(C10 H8N2 O4) (phen) (NO3 ) (H2 O) 2 ]·H2 O .该配合物属单斜晶系 ,空间群为P2 1/c,晶胞参数a =1 5 2 4( 3 )nm ,b =1 10 18( 19)nm ,c =1 468( 3 )nm ,β =92 2 8( 2 )° ,V =2 4 63 ( 7)nm3 ,Z =4,μ =3 10 0mm-1,Dc=1 83 1g/cm3 ,F( 0 0 0 ) =13 40 ,R =0 0 3 14 ,wR =0 0 660 ,GOF =0 966.测试结果表明 ,该单晶结构为镝的 9配位配合物 ,其中一个 2 羰基丙酸水杨酰腙分子以羧基氧、酰胺基中的羰基氧和CN中的氮与Dy3 + 三齿配位 ,形成两个稳定的共边五元环 ,一个 1,10 菲啉分子以二齿方式配位、一个硝酸根和两个水分子也同时参与配位 ,在空间呈扭曲的单帽四方反棱柱 ,而在配合物周围还有一个游离的水分子 .发光性能测试表明配合物具有很好的荧光性能     

3-羟基-1-金刚烷甲酸轻稀土配合物的合成、晶体结构及与DNA作用

以3-羟基-1-金刚烷甲酸(Hhata=C11H16O3),邻菲啰啉(phen)和稀土硝酸盐为原料,合成了7个轻稀土配合物(1)～(7)[RE2(hata)6(phen)2].4H2O(RE=La(1),Ce(2),Pr(3),Nd(4),Sm(5),Eu(6),Gd(7))。其中(1)为单晶样,其余6个样为粉末样;用元素分析、红外光谱、摩尔电导、热重分析等手段表征了配合物;用单晶X射线衍射法测定了(1)的晶体结构,该配合物[La2(hata)6(phen)2].4H2O(C90H114La2N4O22)属于单斜晶系,空间群P2(1)/c,a=1.33979(13)nm,b=2.6395(2)nm,c=1.31321(14)nm,β=112.174(4)°,V=4.3005(7)nm3,Z=2,Mr=1881.67,F(000)=1944.0,Dc=1.453 g.cm-3,μ(Mo Kα)=1.056 mm-1。结果表明:两个镧原子与两个邻菲啰啉中的4个氮原子和6个3-羟基-1-金刚烷甲酸根中的羧基氧原子配位,中心原子的配位数为9。用溴化乙锭荧光探针法测试了7个配合物对EB-DNA复合体系的荧光猝灭效应,实验结果显示配合物均与DNA发生了不同程度的插入作用。     

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。     

Syntheses and Crystal Structures of Two Co(II) Coordination Polymers with 4,4'-(Hexafluoroisopropylidene)bis(benzoic acid)

Two new one-dimensional zigzag chain coordination polymers,[Co(hfipbb)(2,2'-bpy)(H2O)2]n 1 and [Co(hfipbb)(1,10-phen)(H2O)]n 2,have been synthesized under hydrother-mal reactions from CoCl2.6H2O,4,4'-(hexafluoroisopropylidene)bis(benzoic acid) and 2,2' -bipyridine or 1,10-phenanthroline ligands,respectively. Single-crystal X-ray analyses revealed that the zigzag chains of 1 and 2 are linked into three-dimensional supramolecular networks by both O-H···O hydrogen-bonds and π···π stacking interactions. Crystal data for 1:C27H20CoF6N2O6,Mr=641.38,orthorhombic,space group Pnna,a=9.3820(19),b=27.366(6),c=10.106(2) ,V=2594.8(9) 3,Z=4,Dc=1.642 g/cm3,F(000)=1300,μ=0.752 mm-1,R=0.0311 and wR=0.0924. Crystal data for 2:C29H18CoF6N2O5,Mr=647.38,monoclinic,space group P21/n,a=7.7626(16),b=29.446(6),c=11.281(2) ,β=93.98(3)°,V=2572.3(9) 3,Z=4,Dc=1.672 g/cm3,F(000)=1308,μ=0.757 mm-1,R=0.0403 and wR=0.0820.     

RE(CCl_3COO)_3(Phen)_2·nH_2O混配配合物的合成、性质及晶体结构

利用水和乙醇混合溶剂合成了稀土三氯醋酸盐与2份1,10-邻菲绕啉(phen)配合物RE(CCl_3COO)_3(phen)_2·nH_2O(RE=Nd,Sm,n=0;RE=Eu,n=2)的单晶.结构测定表明,Nd(CCl_3COO)_3(phen)_2为三斜晶系,每个三氯醋酸盐均以双齿配位,2个phen亦为双齿配位,故配位单元中钕为10配位;Eu(CCl_3COO)_3(phen)_2·2H_2O为单斜晶系,1个三氯醋酸根在外界,2个三氯醋酸根为单齿配位,2个phen为双齿配位,另有2分配位水,故配位单元中Eu为8配位.     

3-羟基-1-金刚烷甲酸钴邻菲咯啉配合物的合成和晶体结构

以硫酸钴、邻菲咯啉(phen)和3-羟基-1-金刚烷甲酸(HOC10H14COOH)为原料,合成了配合物[Co(HOC10H14COO)2(H2O)(phen)].H2O;利用元素分析、红外光谱、热重分析对产物进行了表征,采用单晶X射线衍射方法测定了其晶体结构.结果表明,所合成的配合物C34H42N2O8Co属于单斜晶系,空间群C2/c,a=2.69798(7)nm,b=1.14319(3)nm,c=2.29092(6)nm,β=120.498(1)°,V=6.0883(3)nm3,Z=8,Mr=665.63,F(000)=2808,Dc=1.452g.cm-3,μ(Mo-Kα)=0.765mm-1;R1=0.0805,wR2=0.2209.其通过氢键和π-π堆积作用相结合,形成稳定的二维超分子结构.     

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.     

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。     

X-ray structure characterization of palladium(II) ternary complexes of pyridinedicarboxylic and phthalic acid with phenanthroline and bipyridine

The crystal structures of the series of four ternary complexes, [Pd(phen)(2,6-PDCA)].4H(2)O (1) (phen=1,10-phenanthroline; 2,6-PDCA=2,6-pyridinedicarboxylic acid), [Pd(bpy)(2,3-PDCA)].3H(2)O (2) (bpy=2,2'-bipyridineand; 2,3-PDCA=2,3-pyridinedicarboxylic acid) and [Pd(phen)(PHT)].2.5H(2)O (3) (PHT=o-phthalic acid ) and [Pd(bpy)(PHT)].1.5H(2)O (4), are determined and the coordination modes of palladium(II) ternary complexes are characterized. All complexes take the mononuclear Pd(II) complexes, in which central Pd(II) atom of each complex has a similar distorted square-planar four coordination geometry. In all complexes, the aromatic heterocyclic compounds, phen and bpy, behave as a bidentate N, N' ligand. In the complex 1 and 2, 2,6-PDCA and 2,3-PDCA behave as a bidentate N, O ligand, and in complex 3 and 4, PHT behaves as a bidentate O, O' ligand.     

Synthesis and crystal structure of a new copper (II) complex,designed to produce efficient successor of Cu2O,toward synergy of adsorption and photodegradation of MB

A new copper (II) coordination complex formulated as [Cu (dipic)(phen)(2-MePy)]. 2H₂O ( 1 ) where phen = 1, 10-phenanthroline, dipic²⁻ = pyridine-2,6-dicarboxylato and 2-MePy = 2-methyl pyrrole was synthesized through a simple and environment-friendly reaction under ultrasound irradiation. Also, complex 1 was synthesized by hydrothermal process at 120 °C for 3 days. The corresponding structure of complex 1 was characterized by elemental analysis, atomic absorption spectroscopy (AAS), inductively coupled plasma (ICP), conductivity measurement, Fourier-transform infrared spectroscopy (FT-IR), Raman spectroscopy, ultraviolet–visible spectroscopy (UV–Vis), thermal gravimetric analysis (TGA), differential thermal analysis (DTA), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM) and fluorescence. The crystal structure of the hydrothermally synthesized complex was characterized by single crystal X-ray diffraction (SC-XRD(, which revealed a triclinic structure. In the remainder of this study, the Cu₂O nanoparticles have been prepared via thermal decomposition of hydrothermal and ultrasound complexes and characterized by ICP, FT-IR, powder X-ray diffraction (XRD), SEM and N₂ adsorption/desorption. Adsorption and visible-light-driven photocatalytic capabilities of two synthetic Cu₂O were investigated in the removal of MB from water. The result showed that the synthesized catalysts have good catalytic activity and the photocatalytic degradation is more effective in dye removal of MB compared with the adsorption.     

[Co(Phen)2(H2O)2](HL)NO3·3H2O的合成及晶体结构

在水溶液中,以邻菲咯啉、丁二酸与硝酸钴为原料合成了一个新的超分子化合物[Co(Phen)2(H2O)2].(HL).(NO3).3H2O,并经元素分析、IR、X射线单晶衍射分析进行了结构表征.结构分析表明,晶体属三斜晶系,P1-空间群,a=0.968 0(2)nm,b=1.370(3)nm,c=1.394 9(3)nm,α=61.714(3)°,β=71.495(4)°,γ=79.575(4)°,V=1.543 7 nm3,Z=2,ρ=1.481 g/cm3,C28H31CoN5O12,Mr=688.51,F(000)=714 andμ=0.627 mm-1,7 754个独立衍射点中,5 428个可观察点满足I≥2σ(I),R1=0.074 5,wR2=0.210 7.晶体中[Co(Phen)2(H2O)2]2+通过π-π相互作用堆积成二维层状结构,层间通过氢键作用构成三维超分子.     

Synthesis and Crystal Structure of a Two-dimensional Framework Supramolecular Complex [Mn(phen)(DPZDA)(H_2O)]·2H_2O

1INTRODUCTION Crystal engineering has captured the interest of re-searchers these years[1,2].Especially,supramolecular chemistry based on weak interactions(hydrogen bond,π-πstacking,C–H···O interaction,ion-πinter-action and hydrophobic interaction,et al.)is one of the most hottest studying fields[3～5].So far,in this field,intensive endeavors have been paid to the synthesis of novel functional complexes possessing catalysis,non-linear optical property,magnetism and molecular recog…     

Hydrothermal Synthesis,Crystal Structure and Thermal Analyses of Pyrazine-2,3-dicarboxylic Acid Bridged Co(II) Coordination Polymer of _∞~2[Co(phen)(μ-L)_(3/3)]·H_2O (H_2L = Pyrazine-2,3-dicarboxylic Acid)

1 INTRODUCTION Molecular assembly and supramolecular che-mistry are young and rapidly growing subjects andhave attracted great attention. Microporous materialsbuilt up by organic ligands and metal ions have po-tential applications in catalysis, chemical absorption,magnetism and electronic conductivity[1～3]. Multi-dentate organic ligands are good building blocks,such as 1,2,4,5-benzene tetracarboxylic acid (BT-CA), 1,3,5-benzene tricarboxylic acid, terephthalicacid, 1,10-phenanthrol…     

溴化二水二(皮考林酰胺)合钴配合物的合成及晶体结构

用皮考林酰胺、六水合硝酸钴和苄基溴反应制得一种新配合物[(C6H6N2O)2Co(H2O)2].B r2,通过红外光谱、元素分析及X射线晶体衍射对化合物进行了表征.结构分析结果表明,配合物属单斜晶系,P2(1)/n空间群,晶胞参数为:a=0.647 61(5)nm,b=1.026 43(9)nm,c=1.264 14(11)nm,β=93.823 0(10),°V=0.838 44(12)nm3,Z=4,Dc=1.977 g/cm3,μ=5.812 mm-1,F(000)=490,R1=0.071 0,wR2=0.251 6.配合物中,Co(Ⅱ)离子为六配位的八面体构型;相邻单元间通过N—H…B r和O—H…B r氢键相互连结而形成三维网状结构.     

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 …     

十一烯酸邻菲咯啉铜(Ⅱ)配合物的合成、表征、晶体结构及与DNA作用

A copper(Ⅱ) complex Cu(C₁₁H₁₉O₂)₂(phen)(H₂O), (C11H19O₂=undecylenic acid, phen=1,10-phenanthroline), was synthesized and characterized by elemental analysis, IR and TG-DTG. Its crystal structure was determined by single crystal X-ray diffraction method. The complex, C₃₄H₄₈N₂O₅Cu, crystallizes in the triclinic system, space group P1. The interaction of complex with DNA was also studied by ethidium bromide (EB) fluorescence spectroscopy. CCDC: 729209.