模板分子诱导的微孔镧系-2-羧基肉桂酸超分子配合物的合成与结构

由水热法合成了2个微孔镧系超分子配合物[Ln(CCA)(OH)(phen)(H₂O)]_n·n(phen)·nH₂O(Ln=Yb, 1;Er, 2;H₂CCA=2-羧基肉桂酸;phen=1, 10-菲啰啉), 并用元素分析、IR及X-射线单晶衍射对其进行了表征。晶体结构研究表明, 2个配合物都是由配体2-羧基肉桂酸连接而形成的一维双链结构, 该链状结构通过氢键和π-π堆积作用扩展为具有微孔结构的超分子。1, 10-菲啰啉在微孔结构的形成过程中起到了模板剂的作用。     

基于L-O-磷酸丝氨酸配合物[Cu(OPSer)(phen)(H2O)]·3H2O的合成、结构和性质

合成了铜(Ⅱ)的手性单核配合物[Cu(OPSer)(phen)(H2O)]·3H2O(1)(H2OPSer=L-O-磷酸丝氨酸;phen=1,10-邻菲啰啉)。通过元素分析、红外光谱、热重分析和磁性对配合物进行表征,并利用单晶X-射线衍射法测定其结构。铜(Ⅱ)具有变形四方锥的配位环境,分别与1个L-O-磷酸丝氨酸离子的1个氮原子和氧原子、1个1,10-邻菲啰啉分子的2个氮原子以及1个配位水分子的氧原子配位。配合物每个分子单元通过氢键连接成三维超分子结构,分子间存在π-π堆积作用。在1.8~300 K范围内磁性测定表明:配合物1中存在铁磁耦合相互作用,经理论拟合:g=2.07,zJ′=0.044。     

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。     

柔性二元羧酸桥联双核镉(II)配合物的合成及晶体结构研究

晶体工程是根据分子堆积和分子间的相互作用,将超分子化学的原理、方法以及控制分子间作用的策略用于晶体,以设计出结构新颖、具有独特的物理性质和化学性质的新晶体[1].超分子间的非共价作用主要包括氢键 [2]、π-π堆积作用 [3]、阳离子-π作用和疏水缔合等,通过选择不同结构的配体,使其在配合物中产生多种非共价作用,是实现从分子到材料的一条重要途径.在配位超分子化合物的设计中,柔性配体相对于刚性配体使用较少[4].α,ω-二元脂肪羧酸根[-OOC-(CH)2n -COO-]具有C-C单键骨架和4个终端羧酸氧原子,单键展现出优良的挠性,而羧基有多种配位方式[5,6].如果再引入端基配体邻菲啰啉,邻菲啰啉的的刚性与二元脂肪羧酸根的柔性进行有机结合,可能形成结构新颖的超分子体系[7,8].本文以镉(II)为中心离子,分别以丁二酸和戊二酸作为第一配体,以邻菲啰啉作为端基配体,在常温下合成了配合物 [Cd2(phen)2(succ)(H2O)2](NO3-)2 ·3H2O (1)和[Cd2(phen)2(glut)2][Cd2(phen)2(Cl-)2]·2NO3-·14H2O(2)(succ =丁二酸,glut=戊二酸,phen=邻菲啰啉).X-射线单晶衍射测试表明,配合物1由丁二酸根单齿桥联两个Cd2+形成双核单元,进一步由氢键桥联成一维链状结构.配合物2含有两个独立结构,分别由戊二酸根和CI-桥联为双核单元,相邻的双核独立单元之间依靠氢键和π-π堆积作用构筑成二维网状结构.     

[Ag(4,4′-bpy)]~+及[Zn(phen)_2(H_2O)_2]~(2+)两种配合物的合成、结构与荧光性质

用水热法和溶液法分别合成了2个新的配合物{[Ag(4,4′-bpy)]·3-HSBA.H2O}n(1)和[Zn(phen)2(H2O)2]·(A-2,5-DSA)·3H2O(2)(3-HSBA=3-羧基苯磺酸根,A-2,5-DSA=苯氨-2,5-二磺酸根,4,4′-bpy=4,4′-联吡啶,phen=1,10-邻菲咯啉),用X-射线单晶衍射结构分析方法测定了其晶体结构。配合物1是一维链状结构。在1个不对称单元中包含1个[Ag(4,4′-bpy)]+阳离子,1个3-羧基苯磺酸根阴离子和1个晶格水分子。Ag髣离子与2个4,4′-联吡啶的2个氮原子配位。配合物2是单核结构。在1个不对称单元中包含1个[Zn(phen)2(H2O)2]2+阳离子,1个苯氨-2,5-二磺酸根阴离子和3个晶格水分子。Zn髤离子与2个1,10-邻菲咯啉的4个氮原子和2个水氧原子配位。配合物1和2中,配位阳离子、抗衡阴离子以及晶格水分子之间存在丰富的氢键,进而构筑成超分子网络结构。配合物的荧光均来自于配体的π-π*电子跃迁。     

[Ag(4，4′-bpy)]+及[Zn(phen)2(H2O)2]2+两种配合物的合成、结构与荧光性质

用水热法和溶液法分别合成了2个新的配合物{[Ag(4,4′-bpy)]·3-HSBA.H2O}n(1)和[Zn(phen)2(H2O)2]·(A-2,5-DSA)·3H2O(2)(3-HSBA=3-羧基苯磺酸根,A-2,5-DSA=苯氨-2,5-二磺酸根,4,4′-bpy=4,4′-联吡啶,phen=1,10-邻菲咯啉),用X-射线单晶衍射结构分析方法测定了其晶体结构。配合物1是一维链状结构。在1个不对称单元中包含1个[Ag(4,4′-bpy)]+阳离子,1个3-羧基苯磺酸根阴离子和1个晶格水分子。Ag髣离子与2个4,4′-联吡啶的2个氮原子配位。配合物2是单核结构。在1个不对称单元中包含1个[Zn(phen)2(H2O)2]2+阳离子,1个苯氨-2,5-二磺酸根阴离子和3个晶格水分子。Zn髤离子与2个1,10-邻菲咯啉的4个氮原子和2个水氧原子配位。配合物1和2中,配位阳离子、抗衡阴离子以及晶格水分子之间存在丰富的氢键,进而构筑成超分子网络结构。配合物的荧光均来自于配体的π-π*电子跃迁。     

新型稀土配位聚合物[Ce(tda)(ox)0.5(phen)]n的合成及拓扑结构

利用混合配体(H2tda=亚硫基二乙酸,H2ox=乙二酸,phen=1,10-菲咯啉)与CeCl3.5H2O反应,合成了新型稀土配合物[Ce(tda)(ox)0.5(phen)]n,单晶结构分析表明:配合物以共边的多面体[Ce2O12N4]为基本单元构筑二维结构,并通过π-π堆积作用拓展为三维超分子体系。该二维结构具有(4,5)连接的(46)(4.466)2拓扑结构,在拓扑结构中稀土离子呈现不寻常的5连接点。     

两个含有2,6-二氟苯甲酸配体稀土配合物的合成及晶体结构

利用2,6-二氟苯甲酸和1,10-菲咯啉作为配体分别与Tm^3+、Yb^3+离子在常温下反应,制得2个稀土配合物[Tm(dfba)2(phen)(μ2-dfba)]2 (1)和[Yb(dfba)2(phen)(μ2-dfba)]2 (2)(dfba-=2,6-二氟苯甲酸根,phen=1,10-菲咯啉)。用元素分析、红外光谱对2个稀土配合物进行了表征,并用单晶X射线衍射确定了配合物的晶体结构;测定了配合物1和2的热稳定性。结构分析表明配合物1和2具有相似的晶体结构。每个Ln^3+与2个dfba-配体和1个phen分子配位,形成[Ln(dfba)2(phen)]+结构单元,[Ln(dfba)2(phen)]+单元再通过2个不同的dfba-配体桥联形成双核分子[Ln(dfba)2(phen)(μ2-dfba)]2(Ln=Tm,Yb)。     

含氟二羧酸和含氮配体与过渡金属(Ⅱ)配合物的合成、表征及晶体结构

水热法合成了5个新的配位聚合物:[Cd(TFSA)(2,2’-bpy)2]n(1),[Mn(HFGA)(phen)2]n(2),[Co(TFSA)(bpp)2(H2O)2]n(3),[Zn(TFSA)(bpp)2(H2O)2]n(4)和[Cu(HFGA)(phen)]n(5)(TFSA=四氟丁二酸,HFGA=六氟戊二酸,2,2’-bpy=2,2’-联吡啶,phen=1,10-邻菲啰啉,bpp=1,3-二吡啶基丙烷),通过X射线单晶衍射确定了配合物的晶体结构.配合物1和2具有相似的1D链结构,四氟丁二酸和六氟戊二酸以两个单齿羧基氧原子分别配位于Cd2+和Mn2+离子,2,2’-联吡啶和1,10-邻菲啰啉分别螯合配位于Cd2+和Mn2+离子.配合物3和4具有相似的1D链结构,1,3-二吡啶基丙烷以两个端基氮原子桥联金属离子,四氟丁二酸和六氟戊二酸分别以单齿方式配位.配合物5是具有{4.82}拓扑的2D网结构,六氟丁二酸配体通过单齿/双齿-桥联模式连接Cu2+离子.5个配合物均通过分子间弱作用进一步构筑成3D超分子结构.     

两个由1H-苯并三氮唑-1-乙酸构筑的镉、银配合物的合成及晶体结构

合成了2个配位聚合物{[Cd(btaa)(phen)(CH3COO)].H2O}n(1)和{[Ag2(btaa)(4,4-bpy)2](NO3).2H2O}n(2)(Hbtaa=1H-苯并三氮唑-1-乙酸,phen=1,10-邻菲啰啉,4,4-bpy=4,4-联吡啶),采用单晶X-射线、红外光谱、元素分析和热重分析对配合物进行了表征。配合物1中的镉离子通过1H-苯并三氮唑-1-乙酸根桥连成一维螺旋链状结构。在配合物2中,银离子被4,4-联吡啶连接成一维链状结构,这些一维链通过1H-苯并三氮唑-1-乙酸根桥连以及Ag...Ag作用和π-π堆积连接成一维梯子状结构。此外,还研究了配合物1的荧光性质。     

Hydrothermal syntheses,crystal structures and luminescence properties of two lanthanide dinuclear complexes with hexafluoroglutarate

Two complexes [Ln₂(hfga)₂(phen)₄(H₂O)₆] · hfga · 2H₂O (H₂hfga = hexafluoroglutaric acid, phen = 1, 10-phenanthroline, Ln=Tb, 1; Eu, 2) were synthesized under hydrothermal conditions and their structures determined by X-ray crystallography. The complexes consist of dinuclear units with an inversion center. Each Ln(III) is nine-coordinate with two carboxylate oxygens from two hfga ligands, three oxygens from water and four nitrogens from two phen molecules. Two carboxylate groups of one hfga adopt monodentate coordination to Ln(III) as a long bidentate bridge linking two Ln(III) ions to form a dimer. Ln(III) ··· Ln(III) distances of 9.027(3) Å for 1 and 9.043(3) Å for 2 were observed. Both complexes emit strong fluorescence and show characteristic emission of Tb(III) and Eu(III) ions, respectively.     

含二茂铁基的锌配合物的结构及其生物活性

合成了4个含二茂铁基的锌配合物[Zn(FcCOO)(phen)₂]ClO₄·FcCOOH (1)(FcCOO=二茂铁甲酸根,phen=1,10-邻菲咯啉),[Zn(FcCOO)(phen)₂]·ClO₄·H₂O (2),[Zn(FcCOO)(FcCOGly)(phen)]·C₂H₅OH (3)(FcCOGly=二茂铁甲酰化甘氨酸)和[Zn(FcCOGly)₂(phen)]·CH₃OH (4)。用X-射线单晶衍射测定了配合物的晶体结构。对4个配合物的生物活性进行了初步研究,发现配合物的抗菌活性与配合物的配位键强度及phen含量有一定的关系。     

Hydro(solvo)thermal synthesis and structural characterization of three lanthanide–carboxylate coordination polymers based on BDC and/or EDTA

Three lanthanide coordination polymers, [Ln₄(BDC)₆(H₂O)₂] _n (Ln = Er, 1; Ln = Tm, 2; BDC = 1,2-benzenedicarboxylate) and {[Nd₂(BDC)(EDTA)(H₂O)₂] · 1.5H₂O} _n , 3, were prepared by hydrothermal synthesis and characterized by elemental analysis, IR spectra, as well as single-crystal X-ray diffraction. The isostructural coordination polymers 1 and 2 exhibit four different coordination modes, which are rarely found in one lanthanide complex. Complex 3 displays a 2-D wave-like network assembled by two polycarboxylate ligands.     

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.     

Three new binuclear copper(II) complexes with isonicotinic acid N-oxide: syntheses,crystal structures and properties

Three new copper(II) complexes with isonicotinic acid N-oxide (HL) and 1,10-phenanthroline (phen) as ligands, [Cu(L)(phen)(H₂O)]₂(NO₃)₂···2H₂O (1), [Cu(L)(phen)(H₂O)]₂(ClO₄)₂···2H₂O (2), and [Cu(L)(phen)Br]₂- [Cu(L)(phen)(H₂O)]₂Br₂···6H₂O (3) have been synthesized and structurally characterized. The structures of all three complexes feature a Cu₂ dimer formed by two Cu(II) ions interconnected by two bridging ligands. Each copper(II) ion has a distorted square pyramidal coordination geometry with elongated axial coordination by an aqua ligand or halogen anion. The isonicotinic acid N-oxide anion is bidentate, being coordinated to two Cu(II) ions through its N-O oxygen and one of its carboxylate oxygen atoms. Magnetic susceptibility measurements show a Curie–Weiss paramagnetic behavior characteristic of one unpaired electron for a copper(II) ion for all three complexes.     

Mixed-ligand lanthanide complexes constructed by flexible 1,3-propanediaminetetraacetate and rigid terephthalate

Abstract

Coordination polymers (CPs) of mixed-ligand lanthanide complexes [Ln₂(1,3-pdta)(TPA)(H₂O)₂]_n·nH₂O [Ln?=?La, 1; Ce, 2; Pr, 3; Nd, 4] (1,3-H₄pdta = 1,3-propanediaminetetraacetic acid; H₂TPA?= terephthalic acid) were hydrothermally synthesized with flexible 1,3-pdta and rigid TPA ligands. Moreover, lanthanide propanediaminetetraacetates [Ln(1,3-Hpdta)(H₂O)]_2n·nH₂TPA·xH₂O [Ln?=?Sm, 5; Gd, 6] with multi-layered structures were also obtained. In 1–4, both 1,3-pdta and TPA coordinate with lanthanide ions through carboxyl oxygen and nitrogen atoms. In 5 and 6, only 1,3-Hpdta coordinates with the central lanthanide ion, where one nitrogen atom in 1,3-Hpdta is protonated, and TPAs are crystallized as H₂TPA with the central multi-layered structures of [Ln(1,3-Hpdta)(H₂O)]_2n through very strong hydrogen bonds [2.504(4) Å]. Solid-state ¹³C NMR analysis of 1 revealed the coordination of carboxyl groups. However, the methylene groups of 1,3-pdta showed an obvious upfield shift, which can be attributed to the effects of the phenyl ring in TPA ligand. The successful synthesis of these mixed-ligand lanthanides provides a rational design of such lanthanide CPs with flexible and rigid ligands.     

4-磺基苯甲酸镍配合物结构多样性与性质研究

本文报道2个镍/4-磺基苯甲酸/1,10-邻菲咯啉配合物的合成、表征、结构和性质。配合物[Ni(4-sb)(phen)(H₂O)₂]·(2H₂O) (1)是单核结构,配合物[Ni(phen)₃]·(4-Hsb)(OH)(8H₂O) (2)是1个阳离子与阴离子复合物。在这2个配合物中金属镍的配位形式均是六配位八面体构型,Ni-N键长相近。2个配合物的扩展结构均为三维网络结构。配合物2中阳离子占据由阴离子与水分子形成的三维网络孔道。配合物2是一个羧基氢未脱去同时又有氢氧根的分子。     

Synthesis and magnetic characterization of Ln(III)–Co(II) complexes with 1,10-phenanthroline ligands

Four heteronuclear complexes, [Ln₂Co₂L₁₀(H₂O)(phen)₂] · n(H₂O) (Ln = La 1, n = 2; Ln = Nd 2, Sm 3, Gd 4, n = 0; HL = α-methylacrylic acid, phen = 1,10-phenanthroline), have been synthesized and characterized by elemental analysis, IR and X-ray diffraction. The complexes with a discrete Co–Ln–Ln–Co tetranuclear molecule are isomorphous in the triclinic space group P 1 and Z = 1, in which all metal ions are bridged by bidentate α-methylacrylato groups. Magnetic measurements of 1, 2 and 3 show antiferromagnetic exchange interaction between paramagnetic centers.     

A series of 3d–4f heterometallic MOFs: syntheses,structures, optical,and electrochemical properties

Abstract

A series of heterometallic metal-organic frameworks (MOFs) employing pyridine-2,6-dicarboxylate and 1,10-phenanthroline as ligands have been synthesized hydrothermally. In isostructural compounds 1–3 [Ln(pydc)₃Cu₂(phen)₄]·I·× H₂O (Ln?=?La (1), Nd (2), Dy (3); x?=?6, 5, 5), the metalloligand [Ln(pydc)₃] assembles with [Cu(phen)₂] units to construct a dodecanuclear cluster via Cu–O bonds and π–π interactions. The clusters are further stacked into three-dimensional supramolecular frameworks with nano-sized cavities. In [La(Hpydc)(pydc)₂Zn(phen)₃]·3H₂O (4), the metalloligand [Ln(Hpydc)(pydc)₂] assembles with [Zn(phen)₃] units to construct a tetranuclear cluster via electrostatic interaction and π–π interaction. This work reveals that the changes of lanthanide metalloligands and the coordination pattern of 3d transition centers would result in significant variation in the final structures. The thermal, optical, and electrochemical properties have been well investigated.