含乳清酸配体的两个单核配合物的合成与晶体结构

0IntroductionInthepastfewyears,themolecular-basedmag-neticpropertiesofheteronuclearcomplexessimultane-ouslycomprisinglanthanideandtransitionmetalionshaveattractedincreasinginterest犤1～6犦.Inourlaborato-ry,wehavesynthesizedsuchtypeofcomplexeswithdifferentcarboxylicbridgingligands犤7～10犦.Asanex-tensionofthisresearcharea,ourpresentworkaimstosynthesizenovelcomplexesofrareearthandtransi-tionmetalbyusingoroticacidasabridgingligand.Inthecourseofourinvestigationtwonewcomp-lexesof犤Cu(C5H2N2O4)(H…     

两个含吡啶取代苯酚配体的铜配合物的合成与晶体结构

以2-[N,N-二(2-吡啶甲基)氨甲基]-6-醛基-4-甲基苯酚(L)为配体,合成了2个单核铜配合物[CuL(CH₃CN)(ClO₄)]ClO₄(1)和cis-[CuL(NCS)₂]·0.5C₄H₈O₂(2),对它们进行了紫外、红外、质谱、元素分析和单晶结构表征。2个配合物都属于单斜晶系,每个铜均为扭曲的八面体构型。作为四齿配体,L通过2个吡啶氮原子,1个叔胺氮原子和1个酚氧原子和铜离子配位。在配合物1中,乙腈和1个ClO₄参与配位,而在配合物2中2个硫氰根离子为顺式配位。     

两个含吡啶取代苯酚配体的铜配合物的合成与晶体结构

以2-[N,N-二(2-吡啶甲基)氨甲基]-6-醛基-4-甲基苯酚(L)为配体,合成了2个单核铜配合物[CuL(CH3CN)(ClO4)]ClO4(1)和cis-[CuL(NCS)2]·0.5C4H8O2(2),对它们进行了紫外、红外、质谱、元素分析和单晶结构表征。2个配合物都属于单斜晶系,每个铜均为扭曲的八面体构型。作为四齿配体,L通过2个吡啶氮原子,1个叔胺氮原子和1个酚氧原子和铜离子配位。在配合物1中,乙腈和1个ClO4-参与配位,而在配合物2中2个硫氰根离子为顺式配位。     

基于草酰胺配体的新型异双核配合物的合成及其晶体结构

以草酰胺铜配合物CuL(H₂L=2,3-二氧-5,6 :13,14-二联苯基-9,10-环己基-1,4,8,11-四氮杂十四环-7,12-二烯烃)为前驱配体,1,10-邻菲啰啉为端接配体,高氯酸锰为金属核心,经回流反应合成了一个新型的异双核配合物［CuLMn(phen)₂］(ClO₄)₂·2CH₃OH(1),其结构和性能经UV-Vis, IR,元素分析,X-射线粉末衍射和X 射线单晶衍射表征。结果表明：1(CCDC: 1 445 582)属三斜晶系,空间群P-1,晶胞参数a=11.298(19) , b=15.17(4) , c=16.71(3) ,α=113.69(3), β=109.30(2), γ=93.08(4), V=2 417(9) ³, Z=2。 1在DMF中的最大吸收峰位于272 nm和361 nm。     

铀-钾异核配位聚合物的合成及晶体结构

在水热反应条件下合成了1种新颖的U(Ⅵ)-K异核配位聚合物[UO2K2(pdc)2(H2O)3]n(H2pdc=吡啶-2,6-二羧酸),通过元素分析、红外、紫外光谱及热重对该配合物进行了表征。单晶结构表明:配合物属于单斜晶系,C2/c空间群;晶胞参数分别为a=1.888 5(6)nm,b=1.490 0(5)nm,c=0.740 2(2)nm,β=111.104(10)°。中心铀及钾原子通过2个氮原子和6个氧原子与吡啶-2,6-二羧酸配体结合。不同的[UO2K2(pdc)2].3H2O单元通过氧原子桥联组成三维链状配位聚合物。配位聚合物中存在π…π相互作用及氢键作用。     

柔性多羧酸配体锶配合物的合成、晶体结构及拓扑学分析

利用水热合成制备了一个新颖的基于柔性多羧酸配体的碱土金属配合物Sr(BuTA)_0.5(H₂O)₂(1)(H₄BuTA=1,2,3,4-丁四酸)。利用元素分析及X-射线单晶衍射对其进行了表征。结构分析结果表明标题化合物1属于单斜晶系,P2₁/c空间群,晶胞参数为a=0.870 03(5) nm,b=0.793 03(5) nm,c=1.268 07(5) nm,β=127.689(3)°,晶胞体积V=0.692 36(7) nm³,Z=4,D_calc=2.290 g·cm^-3,F(000)=468,μ=7.768 cm^-1,R=0.015 8,wR=0.037 7。在化合物1中,每个Sr(Ⅱ)的配位环境为八配位的反四棱柱配位构型。在配合物中金属和配体互相连接形成一个三维的框架结构,其拓扑为(4⁶)₂(4¹².6¹².8⁴)。在其结构中配体是少见的八连接点。对配合物1的热稳定性也做了测试。     

混合配体构筑的Cd~(2+)配合物的合成及其晶体结构

通过溶剂热技术,制得一种新型的Cd~(2+)配合物[Cd(L)_2(ba)_2]_2(1,L=4'-(4-甲基苯)-4,2':6',4″-三联吡啶,Hba=苯甲酸),其结构经IR,元素分析和单晶射线衍射表征。1属单斜晶系,空间群为P2_1/c,晶胞参数a=1.095 5(2)nm,b=1.404 1(3)nm,c=3.045 5(8)nm,β=103.37(3)°,V=4 557.6(18)3,D_c=1.459g·cm~(-3),Z=2,R_1=0.045 5,wR_2=0.094 0[I2σ(I)]。结构分析表明:1为零维双核结构,通过π…π堆积作用拓展为二维层状超分子。     

苯并咪唑基铜配位聚合物定向合成子代配合物：小分子配体取代反应及配合物晶体结构

由配合物作前驱体(简称:前驱体配合物)来制备子代配合物是配合物定向合成的有效方法之一。与一般的有机配体相比,前驱体配合物拥有特定的、相对稳定的结构骨架,并且在一定的反应条件下能够与有机配体之间进行定向自组装,形成具有预期结构的配合物,同时还能把自己的结构特征"遗传"给子代配合物。本论文选择一个一维长链铜配合物{[Cu(bbbm)(CH_3COO)_2]·(CH_3OH)_2}n(Q)[bbbm=1,1’-(1,4-丁基)-二-(1-H-苯并咪唑)]作为前驱体配合物,通过小分子配体的取代、加成反应获得了一个新的子代配合物[Cu(bbbm)(N_3)_2(Py)]n(1)。单晶衍射分析结果显示子代配合物(1)"遗传"了前驱体配合物(Q)的一维长链结构。我们还进一步研究了反应前后配合物的配位方式、bbbm配体构象变化及其催化性能变化。     

桥联异双核配合物的设计和合成

异双核配合物在生命科学和分子磁性材料研究领域起着重要作用，但它的合成却难度较大。本文介绍四种常用、有效的合成方法。     

以芳香羧酸及双咪唑基化合物为配体的钴配合物的合成和晶体结构

以硝酸钴、4,4’-（六氟异丙基）二（苯甲酸）（H₂FBA）和1,2-二咪唑基二甲苯（OBIX）或4,4’-二咪唑基二甲联苯（BIMB）为原料,在水热条件下得到2个结构不同的配位聚合物[Co（OBIX）（FBA）]_n（1）和[Co₂（BIMB）₂（FBA）₂]_n（2）。对它们进行了元素分析、红外光谱分析,并利用X-射线衍射测定了它们的单晶结构。配合物1中2个钴离子通过2个OBIX配体桥连成一个24元大环,它再通过FBA配体连接成一维管状结构,而配合物2中钴离子通过两种配体连接成一维左右两种螺旋结构,2种螺旋结构通过交替互锁形成二维层状结构。结果说明了辅助配体在配合物组装过程中起着非常重要的作用。     

Synthesis and Crystal Structure of a Co（II） Coordination Polymer Derived from a Flexible Bipyridyl Derivative Ligand

1 INTRODUCTION The infinite networks constructed from transition metal complexes have attracted considerable current interest in recent years. The motivation behind this activity has been stimulated by their potential appli- cations in selective inclusion of ions, molecular re- cognition, host-guest chemistry, ion exchange, cata- lysis, electrical conductivity, magnetism, optics and so on[1～4]. It is well known that the diversity in structures and topologies of supramolecules is attri- b…     

Synthesis and Crystal Structure of a One-Dimensional Coordination Polymer Containing Unusual Na_2Cu_2 Tetrametallacyclic Units

ＩｎｔｒｏｄｕｃｔｉｏｎＳｅｌｆ ａｓｓｅｍｂｌｅｄｉｎｆｉｎｉｔｅｃｏｏｒｄｉｎａｔｉｏｎｐｏｌｙｍｅｒｓａｎｄｓｕｐｒａｍｏｌｅｃｕｌｅｓｗｉｔｈｓｐｅｃｉｆｉｃｎｅｔｗｏｒｋｔｏｐｏｌｏｇｉｅｓｈａｖｅａｔｔｒａｃｔｅｄｃｏｎｓｉｄｅｒａｂｌｅａｔｔｅｎｔｉｏｎｄｕｅｔｏｔｈｅｉｒｐｏｔｅｎｔｉａｌａｐ ｐｌｉｃａｔｉｏｎｓａｓｆｕｎｃｔｉｏｎａｌｍａｔｅｒｉａｌｓａｓｗｅｌｌａｓｆａｓｃｉｎａｔｉｎｇｍｏｌｅｃｕｌａｒａｎｄｃｒｙｓｔａｌｓｔｒｕｃｔｕｒｅｓ .Ｗｈｉｌｅｔｈｅｖａｓｔｍａｊ…     

Synthesis and Crystal Structure of a Novel Manganese Coordination Polymer Constructed by 3,5-Dimethylbenzoic Acid with 4,4'-Bipyridine

1 INTRODUCTION There has been extensive interest in manganese complexes containing carboxylate ligands due to the richness in structural chemistry and potential appli- cations in catalysis[1～6], for example, some highly efficient manganese catalysis mimics[7, 8]. Further- more, 4,4?-bipy is an excellent bridging ligand, and so far a number of one-, two- and three-dimensional infinite metal-4,4?-bipy frameworks have already been generated[9, 10]. However, of the above-mentio- ned framework…     

Hydrothermal Synthesis and Crystal Structure of a New Three-dimensional Heterometallic Coordination Polymer

A new 3d-4f heterometallic polymer {[Sm2Cu(PDC)2(SO4)2(H2O)6]·2H2O}n 1 has been synthesized by Sm2O3, Cu(SO4)2·5H2O and pyridine-3,5-dicarboxylic acid under hydrothermal conditions. The compound crystallizes in triclinic system, space group P1, with a = 6.352(7), b = 10.040(10), c = 10.315(11) , α = 94.958(14), β = 95.556(7), γ = 99.747(14)°, V = 641.7(12)3, Z = 1, Mr = 1030.63, Dc = 2.651 Mg/m3, μ = 5.615 mm-1, F(000) = 491, the final R = 0.0491 and wR = 0.1345 for 2098 observed reflections with I > 2σ(I). The compound is a three-dimensional network structure in which infinite lanthanide-carboxylate chains are linked by [Cu(SO4)2]2- metalloligands to form a mixed-metal coordination network.     

Synthesis and Crystal Structure of a Puckered Rhombus Grid-like Coordination Polymer with Bridging Ligand Containing Sulfanyl Linker

Introduction The design and construction of metal-organic frameworks (MOFs), obtained by metal-directed self-assembly from labile metal centers and multidentate bridging ligands, is a rapidly developing area of su-pramolecular chemistry.1-3 Besides the aesthetic struc-tural and fascinating functional motifs, they are of in-terest both for understanding the mechanisms of the assembly process and for the host-guest chemistry asso-ciated with their large central cavities.4-13 It has been documen…     

一维链状锰配位聚合物[Mn(3,5-Me2PhCO2)2(phen)]n的合成与晶体结构

A manganese coordination polymer [Mn(3,5-Me₂PhCO₂)₂(phen)]_n(phen=1,10-phenanthroline) has been synthesized by hydrothermal methods. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a=0.770 3(4) nm, b=1.145 2(6) nm, c=1.537 0(9) nm, α=78.182(9)°, β=77.170(9)°, γ=89.784(9)°, V=1.292 8(12) nm³, Z=2, M_r=533.47, D_c=1.370 g·cm^-3, μ=0.549 mm^-1, F(000)=554, R_int=0.043 4, R=0.060 8 ,wR=0.148 4. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from phen and four oxygen atoms from four 3,5-dimethylbenzolate molecules, completing an octahedral geometry. And the title complex forms one-dimensional chain structure through bridging 3,5-dimethylbenzolate molecules. CCDC: 642920.     

Synthesis and Crystal Structure of a New Complex Constructed from a Flexible Tetrapyridyl Ligand

The title complex [Cd2(NO3)2(OCH3)2(TPOM)2]·8H2O (TPOM=tetrakis(4-pyri- dyloxymethylene) methane) has been synthesized and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. It crystallizes in the orthorhombic crystal system Ccca with a=17.125(2), b=40.751(3), c=24.938(2) , β = 90.00o, V= 7403(3) ·3, C26H27N5O8Cd, Mr = 649.93, Z=16, F(000) = 5280, Dc = 0.992 mg/m3, μ(MoKα) =0.538 mm-1, S=1.080, the final R = 0.0533 and wR=0.1449 for 6627 observed reflections (I>2σ(I)). The crystal structure shows that each Cd atom is coordinated to four pyridyl nitrogen atoms from four TPOM ligands and each tetrahedral TPOM ligand links up four Cd atoms into a 2-fold interpenetrating 3D framework. The TG analysis shows that the framework of the title complex is stable up to 300 ℃.     

Synthesis and Crystal Structure of a One—Dimensional Corrdination Polymer Containing Unusual Na2Cu2 Tetrametallacyclic Units

A unique coordination polymer, {[CuLNa(ClO₄)]·H₂O}_n (1), was isolated from the solution containing sodium perchlorate and the neutral macrocyclic oxamidocopper(II) complex [CuL] (H₂L = 2,3‐dioxo‐5,6:13, 14‐dibenzo‐7, 12‐bis(ethoxycarbonyl)‐1, 4, 8, 11‐tetraazacyclotetradeca‐7, 11‐diene). The complex is composed of [Na₂Cu₂] tetrametallacycles bridged by perchlorate ions to form infinite one‐dimensional chains which are stacked via τ‐τ interactions and weak coordination bonds to result in a two‐dimensional supramolecular network. The perclorate ions were found to coordinate to sodium atoms in the unusual bridging chelating tridentate mode of μ₂‐(O:O′,O″).     

新型含2-噁唑啉基三角架配体-银(I)一维配位聚合物的合成与结构

通过含2-噁唑啉基三角架配体1,3,5-三(2-噁唑啉基)苯(L)与三氟醋酸银反应合成了配合物[Ag₄(L)₂(CH₃CN)₂(CF₃CO₂)₄]_n (1), 并利用元素分析、电喷雾质谱、X射线单晶衍射等方法对其进行了表征. 晶体结构解析结果显示配合物1属三斜晶系, 空间群P-1, a＝0.83731(6) nm, b＝1.22828(9) nm, c＝1.33997(10) nm, α＝102.9760(10)°, β＝107.3050(10)°, γ＝93.8600(10)°, Z＝1, R＝0.0365, wR₂＝0.0929. 该配合物是由[Ag₄(L)₂(CF₃CO₂)₂]^2＋笼状结构单元通过另外两个三氟醋酸根双桥连形成的一维链状结构. 相邻的链间通过C—H…O氢键进一步扩展为二维网状结构. 电喷雾质谱研究结果显示在实验条件下, 溶液中配合物1是以聚合状态存在的.