(英)两个基于大环配体五员瓜环的异核金属配合物的合成及晶体结构

设计并合成了两个五员瓜环(Q[5])桥联K+和Na+形成的新型配合物[K(H2O)2Na(H2O)Q[5]](ClO4)2·6H2O(1),[KNaH(H2O)4Q[5]]n(ClO4)3n·3nH2O(2)。利用单晶X射线衍射进行结构测定,结果表明,配合物1中Q[5]起着一个双五齿配体的作用,每个端口的5个羰基氧原子分别和钾离子和钠离子配位,形成分子胶囊;配合物2中每个钾离子分别通过与相邻的2个Q[5]端口的相邻一对羰基氧原子配位,使得配合物形成一维链状结构,同时Q[5]还提供1个羰基氧原子与Na+配位,氢键使得配合物形成三维超分子结构。     

抗衡阴离子PF6-调控的1,3-丙二胺缩邻香兰素镧(Ⅲ)配合物的合成和晶体结构

通过柔性配体1,3-丙二胺缩邻香兰素(H2L)与和La(NO3)3.6H2O反应,合成了1个由2个H2L桥连的双核稀土配合物[La2(NO3)6(H2L)2].CH2Cl2(1),该配合物与(NH4)(PF6)继续反应生成了1个由2个NO3-离子桥连的双核配合物[La2(NO3)2(H2L)4](PF6)4.4H2O.2CH2Cl2(2),X-射线单晶衍射分析确定了2个配合物的晶体结构。配合物1和2为结构完全不同的2个双核结构,因抗衡阴离子PF6-有去阴离子的作用,配合物1中的NO3-离子被配体取代,导致配合物1的结构翻转,形成了1个新颖的双核结构2。     

两个基于五员瓜环的异核金属配合物的合成及晶体结构(英文)

设计并合成了两个五员瓜环(Q[5])桥联K+和Na+形成的新型配合物[K(H2O)2Na(H2O)Q[5]](ClO4)2·6H2O(1),[KNaH(H2O)4Q[5]]n(ClO4)3n·3nH2O(2)。利用单晶X射线衍射进行结构测定,结果表明,配合物1中Q[5]起着一个双五齿配体的作用,每个端口的5个羰基氧原子分别和钾离子和钠离子配位,形成分子胶囊;配合物2中每个钾离子分别通过与相邻的2个Q[5]端口的相邻一对羰基氧原子配位,使得配合物形成一维链状结构,同时Q[5]还提供1个羰基氧原子与Na+配位,氢键使得配合物形成三维超分子结构。     

1,3-亚丙基双(草胺酸根)桥联的Gd(Ⅲ)Cu(Ⅱ)Gd(Ⅲ)三核配合物

合成和表征了三种新的异三核配合物, {[Gd(L)2]2[Cu(pba)]}(ClO4)4,其中pba为1,3-亚丙基双(草胺酸根)和L表示1,10-菲咯啉(phen),5-硝基-1,10-菲咯啉(NO2-phen)或2,2'-联吡啶(bpy)。基于{[Gd(phen)2(ClO4)]2[Cu(pba)]}(ClO4)2.2H2O的变温磁化率测量(4.1~300K),求出交换积分J=3.576cm^-^1。表明在铜(Ⅱ)和钆(Ⅲ)离子间存在铁磁性偶合。     

对乙酰氨基苯甲酸和含氮配体构筑铜、锌配合物的合成、结构及性质研究(英文)

利用对乙酰氨基苯甲酸(HPABA)和邻菲咯啉(phen)、硝酸铜在DMF/CH3OH/H2O溶液中合成了单核铜配合物[Cu(PABA)(phen)(H2O)2]·(NO3)·H2O(1),然后又和4,4′-联吡啶(4,4′-bpy)、硝酸锌在DMF/CH3OH/H2O溶液中获得配位聚合物{[Zn(PABA)2(4,4′-bpy)]·4H2O}n(2)。根据X射线衍射分析结果,配合物1中每个铜离子周围有2个氮原子和3个氧原子与之配位形成畸变的四方锥配位构型,然而在配合物2中,六配位八面体构型的锌离子通过配体4,4′-联吡啶扩展为一维Zigzag型链。分别对这两个配合物的热稳定性和电化学性质进行了研究。     

对苯二甲酸、2-(3-吡啶基)苯并咪唑配位聚合物的合成、晶体结构和发光

在水热条件下,对苯二甲酸(H2Bdc)和2-(3-吡啶基)苯并咪唑(3-PyHBIm)与Cd(NO3)2、Zn(NO3)2反应,得到配合物{[Cd(3-PyHBIm)(Bdc)(H2O)2](H2Bdc)1/2}n (1)、[Zn(3-PyHBIm)2(Bdc)(H2O)2]n (2)。单晶X-射线衍射结构分析表明,两个化合物均呈一维聚合结构,3-PyHBIm配体采用吡啶氮原子单齿配位。在配合物1中,对苯二甲酸根作为四齿配体,桥联Cd(II)离子,形成一维锯齿链状配位聚合物,两个水分子呈顺式配位。该化合物含有对苯二甲酸客体分子,通过强的氢键,构成三维超分子框架。在配合物2中,对苯二甲酸根作为双齿配体,结合Zn(II)离子,形成直线链状配位聚合物,两个水分子呈反式配位。两个配位聚合物都对热稳定,在固体状态下,呈蓝色发光。     

两个单核镍含氮配体配合物的合成、晶体结构及荧光性质(英文)

采用回流法在水溶剂中合成了2个含氮配体单核镍配合物[Ni(phen)2(H2O)2](1,6-nds)·2H2O(1)和[Ni(phen)3](1,6-nds)·10H2O(2)(1,6-nds=1,6-萘二磺酸根离子,phen=1,10-邻菲罗啉)。配合物1中,镍离子与2个1,10-邻菲罗啉和2个水分子配位,形成[Ni(phen)2(H2O)2]2+阳离子。2个没有配位的水分子通过氢键与[Ni(phen)2(H2O)2]2+和1,6-萘二磺酸根离子相互连接形成二维层状结构。配合物2中,镍离子与3个1,10-邻菲罗啉配位,形成[Ni(phen)3]2+阳离子。大量的氢键将自由的水分子和1,6-萘二磺酸根离子连接形成三维网状结构。2个配合物中1,6-萘二磺酸根离子均没有与镍离子配位,只是起到平衡电荷的作用。室温下,配合物显示了较大的荧光发射峰,其最大发射峰分别在443和438 nm。     

三维无限伸展结构稀土配合物K3{[Sm(H2O)7]2Na-[α-SiW11O39Sm(H2O)4]2}·14H2O的合成、结构及性质研究

以Sm2O3,HClO4,NaOH和α-K8SiW11O39·nH2O等为原料合成了组成为K3{[Sm(H2O)7]2Na[α-SiW11O39Sm(H2O)4]2}·14H2O的三维无限伸展结构稀土配合物,并经IR,UV光谱,ICP原子发射光谱,TG-DTA,循环伏安,变温磁化率和X射线单晶衍射等分析手段进行了表征.X射线单晶衍射测定表明,该化合物属于三斜晶系,Pi空间群,晶胞参数:a=1.2462(3),b=1.2652(3),c=1.8420(4)nm,α=87.45(3),β=79.91(3),γ=82.57(3)°,Z=1,R1=0.0778,wR2=0.1610.结构分析结果显示,sm3+(1)配离子镶嵌在[α-SiW11O39]8-的空缺位置形成[α-SiW11O39Sm(H2O)4]5-亚单元,两个[α-SiW11O39Sm(H2O)4]5-亚单元通过两个Sm(1)-O-W桥互相连接形成标题化合物的二聚体结构单元[α-SiW11O39Sm(H2O)4]210-,相邻的二聚体结构单元又通过两个Sm3+(2)配离子和一个Na+(1)离子桥连成一维链状结构,链与链之间通过K+(1)离子连接成二维网状结构,网状结构又通过K+(2)离子构筑成新奇的三维无限伸展结构.TG-DTA结果表明,标题化合物阴离子骨架分解温度为554℃.循环伏安行为测试表明,标题化合物阴离子在pH=3.1的水溶液中存在两步氧化还原过程.变温磁化率结果表明,在较高温度(110～300 K)时,标题化合物磁性遵循居里-外斯定律,在较低温度(2～110 K)时,存在较强的反铁磁交换作用.     

原位羟基化2,2'-联吡啶类配体及其新颖的铜髣和混价铜(Ⅰ,Ⅱ)超分子构筑的合成(英文)

本文利用水热法合成了两个新型一价铜配合物[Cu2(ophen)2]·H2O的类同质多晶结构(1α和1β)和一个混合价的铜配合物[Cu2(obpy)2(NO3)]·H2O(2)。晶体结构分析表明:1α显现出于无水的类似物[Cu2(ophen)2]相同的堆积方式,1β则形成出新奇的空间堆积。混合价化合物2是完全离域的,通过氢键集聚体[(H2O)2(NO3-)2]将两个[Cu2(obpy)2] 单元连接起来形成哑铃状的四核结构。     

一维镉(Ⅱ)和镍(Ⅱ)配位聚合物的合成、晶体结构、荧光及磁性质（英文）

在水热条件下,用联苯类四羧酸配体(H4L)和菲咯啉(phen)分别与CdCl2·H2O和NiCl2·6H2O反应,合成了2个具有一维链结构的配合物{[M2(μ3-L)(phen)3]·5H2O}n(M=Cd(1),Ni(2)),并对其结构、荧光和磁性质进行了研究。结构分析结果表明2个配合物是异质同心的,属于正交晶系,Pbca空间群。2个配合物具有一维链结构,而且这些链通过O-H…O氢键作用进一步形成了二维超分子网络。研究表明,配合物1在室温下能发出蓝色荧光,配合物2中相邻Ni?髤离子间存在铁磁相互作用。     

Synthesis,structures, and urease inhibition of nickel(II), zinc(II), and cobalt(II) complexes with similar hydroxy-rich Schiff bases

Four new nickel(II), zinc(II), and cobalt(II) complexes, [Zn(L¹)₂]?·?H₂O (1), [Ni(L¹)₂]?·?H₂O (2), [Ni(L²)₂] (3), and [Co(L³)₂]?·?H₂O (4), derived from hydroxy-rich Schiff bases 2-{[1-(5-chloro-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol (HL¹), 2-{[1-(2-hydroxy-3-methoxyphenyl)methylidene]amino}-2-ethylpropane-1,3-diol (HL²), and 2-{[1-(5-bromo-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol (HL³) have been synthesized and characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray determination. Each metal in the complexes is six-coordinate in a distorted octahedral coordination. The Schiff bases coordinate to the metal atoms through the imino N, phenolate O, and one hydroxyl O. In the crystal structures of HL¹ and the complexes, molecules are linked through intermolecular O–H···O hydrogen bonds, forming 1-D chains. The urease inhibitory activities of the compounds were evaluated and molecular docking study of the compounds with the Helicobacter pylori urease was performed.     

New lanthanide-based complexes constructed from cucurbit[6]uril: Synthesis,structures and properties

Three lanthanide-based complexes, {Gd₂(H₂O)₁₀(CB[6])₂}·CB[6]·6Cl·12H₂O (1), {[Gd₂(H₂O)₈CB[6]₂]·(CuCl₄)·4Cl·46H₂O}_n (2), and {Dy₂(NO₃)₂(H₂O)₁₀(CB[6])}·4NO₃·14H₂O (3) (CB[6] = cucurbit[6]uril), were prepared with cucurbit[6]uril (CB[6]). These complexes were characterized by single-crystal X-ray diffraction, elemental analysis, FT-IR spectroscopy, UV–Vis spectroscopy, thermogravimetric analysis and magnetization measurements. Crystallographic results showed that 1 and 3 are dinuclear and crystallize in the triclinic space group Pī, whereas 2 is a 1-D zigzag supramolecular chain that crystallizes in the monoclinic system in C2/c. The results indicated that temperature has a big effect on the supramolecular assemblies and a different structure inducer also leads to the formation of different coordination polymers. Frequency dependence in the ac susceptibility signals was observed in 3.     

Inclusion compounds of cucurbit[8]uril with noble metal polyamine complexes

Inclusion compounds of the macrocyclic cavitand cucurbit[8]uril (CB[8]) with the ruthenium(iii) bis(ethylenediamine) complex {trans-[Ru(en)₂Cl₂]@CB[8]}Cl·27.5H₂O (1), the gold(iii) diethylenetriamine complex {[Au(dien)Cl]@CB[8]}Cl₂·11H₂O (2), and the gold(iii) and platinum(ii) cyclam complexes (H₃O)₅{[Au(cyclam)]@CB[8]}Cl₈·18H₂O (3) and {[Pt(cyclam)]_0.11(H₂cyclam)_0.89@CB[8]}Cl₂·16H₂O (4), respectively, where cyclam is the tetraazamacrocyclic ligand, were synthesized. The inclusion compounds were synthesized both directly starting from CB[8] and the metal complexes with polyamines (en or dien) and by the two-step method with the use of the cyclic polyamine ligand (cyclam) pre-included into the cavity of the macrocycle. The inclusion compounds were characterized by X-ray diffraction (1, 2, and 4), IR spectroscopy, electrospray ionization mass spectrometry, UV-Vis spectroscopy, and thermogravimetric analysis.     

Synthesis and application of a new copper(II) complex containing oflx and leof

Two new copper(II) complexes of [Cu(Ofloxacin)(phen)(H₂O)] · (NO₃) · 2H₂O and [Cu(Levofloxacin)(phen)(H₂O)] · (NO₃) · 2H₂O were obtained and their structures were studies. Both ligands and complexes were assayed against gram-positive and gram-negative bacteria by the in vitro doubling dilutions method. The inhibitory effect of the ligands and complexes on the leukemia HL-60 cell line were measured with the MTT assay method and the liver cancer HePG-2 cell line measured by the SRB method. The results indicated that the complexes have stronger inhibitory effect on HL-60 than on HePG-2. The complex [Cu(Levofloxacin)(phen)(H₂O)] · (NO₃) · 2H₂O (I) has stronger effect on HL-60 than the complex (Cu(Ofloxacin)(phen)(H₂O)] · (NO₃) · 2H₂O (II). The text was submitted by the authors in English.     

Syntheses,Crystal Structures,and Magnetic Properties of Three 1D Chain Metal–Nitroxide Complexes Bridged by ­Flexible Dicarboxylate Anions

Three new one‐dimensional (1D) chain metal–nitroxide complexes {[Cu(NIT4Py)₂(suc)(H₂O)] · 3H₂O}_n ( 1 ), {[Cd(NIT4Py)₂(suc)(H₂O)] · [Cd(NIT4Py)₂(suc)(H₂O)₂] · 3H₂O}_n ( 2 ), and {[Zn(NIT4Py)(glu)(H₂O)] · H₂O}_n ( 3 ) [NIT4Py = 2‐(4′‐pyridyl)‐4, 4, 5, 5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide, suc = succinate anion and glu = glutarate anion] were synthesized and structurally characterized. Single‐crystal X‐ray analyses indicate that the three complexes crystallize in neutral 1D chains in which the metal‐nitroxide units are linked by flexible dicarboxylate anions. The succinate anions only adopt trans configuration in complexes 1 and 2 , whereas the glutarate anion has gauche/anti conformation in complex 3 . Magnetic measurements show that complex 1 exhibits weak antiferromagnetic interactions between the copper ions and the nitroxides.     

Two independent, 1-D metal–organic nanotubes based on rings or helical chain units

Three coordination polymers {[Mn(bte)(NO₂-1,3-bdc)(H₂O)]·H₂O}_n (1), {[Mn(btp)(NO₂-1,3-bdc)(H₂O)]·2H₂O}_n (2), and {[Mn(btb)(NO₂-1,3-bdc)(H₂O)]·H₂O}_n (3) (bte, 1,2-bis(1,2,4-triazol-1-yl)ethane; btp, 1,3-bis(1,2,4-triazol-1-yl)propane; btb, 1,4-bis(1,2,4-triazol-1-yl)butane, NO₂-1,3- H₂bdc, 5-nitroisophthalic acid) were synthesized by combination of bte, btp, and btb, conformationally flexible ligands with different spacer lengths, and the rigid [NO₂-1,3-bdc]^2?. In 1, two [NO₂-1,3-bdc]^2? anions link adjacent [Mn₂(bte)₂] rings to give an independent, 1-D metal–organic nanotube (MONT). The structure of 2 is an undulating 2-D (4,4) network. In 3, the combination of a [Mn(btb)]_n single helical chain and two [Mn(NO₂-1,3-bdc)]_n linear chains assemble an intriguing independent, 1-D MONT. An interesting structural feature of 1 and 3 is that the nitro groups of each 1-D MONT interpenetrate into two adjacent 1-D MONTs to form a 1-D → 2-D interdigitated array. 3-D architectures in 1 and 3 are assembled via hydrogen bond interactions. The luminescent properties and thermal stabilities of 1, 2, and 3 were investigated.     

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.     

2,7-萘二磺酸阴离子导向五元瓜环基超分子自组装体的制备及其荧光检测性能

通过引入2,7-萘二磺酸(2,7-NDA^2-)阴离子作为结构导向剂,与五元瓜环(Q[5])和过渡金属离子(Co²⁺、Ni²⁺、Zn²⁺、Cd²⁺)在水热条件下制备了4种新颖的Q[5]基超分子自组装体(Q[5]-SA),即{[M (H₂O)₄(Q[5])]·(NDA)}·xH₂O (M=Co (1)、Ni (2)、Zn (3))和{[Cd₂Cl₂(H₂O)₄(Q[5])]·(NDA)}·13H₂O (4)。单晶X射线衍射测试结果表明,自组装体1~3同构,其中Q[5]仅一端的部分端口羰基氧原子与金属离子配位形成简单配合物;而4中Q[5]的2个端口均与金属离子Cd²⁺配位形成了一维配位链。在自组装体1~4中,配体2,7-H₂NDA均全脱质子,形成2,7-NDA^2-阴离子平衡体系电荷,但均未能与金属离子配位,而在2,7-NDA^2-阴离子与Q[5]外壁之间的瓜环外壁作用下进一步形成三维超分子结构。此外,还研究了自组装体1和4的荧光传感性能,结果表明它们都能够作为抗生素诺氟沙星(NFX)的比率型荧光探针。     

Syntheses,crystal structures,and fluorescent properties of two d10 metal complexes based on 2-(benzoimidazol-yl)methyl)-1H-1,2,4-triazole and 1,3,5-benzenetricarboxylate

Two d¹⁰ metal complexes, {[Zn(Hbtc)(bmt)]·DMF·5H₂O} _n (1) and {[Cd(Hbtc)(bmt)]·0.5DMF·0.5H₂O} _n (2) (H₃btc?=?1,3,5-benzenetricarboxylic acid, bmt?=?2-((benzoimidazol-yl)methyl)-1H-1,2,4-triazole), have been synthesized under solvothermal conditions by employing bmt and H₃btc. Single-crystal X-ray diffraction shows that Zn(II) ions are connected by bmt with bidentate-bridging coordination and by 1,3,5-benzenetricarboxylate with bis-monodentate coordination leading to the 2D structure of 1. Complex 2 exhibits a 2D layer structure, in which bmt coordinate tridentate-bridging to Cd(II) and 1,3,5-benzenetricarboxylates coordinate to Cd(II) unidentate/chelating. Photoluminescence and thermogravimetric analyses of the two complexes are investigated.     

肉桂酸及其衍生物的Eu(Ⅲ)配合物的合成、结构及荧光性质研究

以肉桂酸C₉H₈O₂(HL)及其衍生物对位取代肉桂酸R-L(R=CH₃,Cl,NO₂,OCH₃,OH)为配体,分别与Eu³⁺配位,得到系列Eu³⁺配合物。X-射线单晶解析结果表明:对甲基肉桂酸铕(1)和对氯肉桂酸铕(2)为一维高分子链,对硝基肉桂酸铕(3)为双核结构。通过FT-IR和UV-Vis光谱分析了配体在配位前后的变化。记录和解析了各配合物的荧光光谱,研究了对位取代基吸电子性和配位小分子对配合物发光性能的影响。