具有三核Cd(Ⅱ)簇单元和螺旋链的脯氨酸类单一手性金属-有机框架材料的合成、 结构和性质

在溶剂热反应条件下, 使用含氮辅助配体1,4-二(4-吡啶基)苯(1,4-DPB)和半刚性脯氨酸衍生物配体(R)-5-(2-羧基吡咯烷-1-羰基)间苯二甲酸[(R)-H₃PIA]或(S)-5-(2-羧基吡咯烷-1-羰基)间苯二甲酸[(S)-H₃PIA]与Cd²⁺构筑了单一手性金属-有机框架材料[Cd_1.5((R)-PIA)(1,4-DPB)_1.5]·0.75H₂O·xGuest(1-D)和[Cd_1.5((S)-PIA)(1,4-DPB)_1.5]·0.75 H₂O·xGuest(1-L). 配合物1-D和1-L呈具有开放孔道的三维柱层式框架结构, 含有三核镉簇单元 Cd₃(CO₂)₆与两种螺旋链构建的波浪形Cd-PIA层. 分别对上述化合物进行了粉末X射线衍射、 热重分析、 圆二色谱和荧光光谱等测试. 测试结果显示配合物1-D和1-L都是以纯晶体的形式存在, 2种配合物的热失重曲线接近, 圆二色谱有明显的正负吸收峰, 符合其对映体的结构特征.     

基于Keggin型杂多酸的无机-有机杂化物的合成和光催化活性

采用水热合成方法制备了2个基于Keggin型杂多酸的无机-有机杂化物, 化学式分别为{[Cu₂(4,4′- bipy)₄(H₂O)₄](SiMo₁₂O₄₀)·18H₂O}_n(1)和{[Cu₂(4,4′-bipy)₄(H₂O)₄](PMo₆W₆O₄₀)·18H₂O}_n(2)(bipy=bipyridine). 结构分析 表明2个化合物同构, Cu²⁺是六配位, 分别与4个4,4′-bipy上的N原子和2个水分子上的O原子结合, 形成 [Cu(4,4′-bipy)₂(H₂O)₂]_n²ⁿ⁺二维层状结构. 杂多阴离子通过静电与配位阳离子[Cu(4,4′-bipy)₂(H₂O)₂]_n²ⁿ⁺作用交叉排列在层间. 通过红外光谱、 粉末X射线衍射和固体紫外-可见漫反射光谱等对化合物的性质进行了表征. 研究了所合成化合物对水溶性染料亚甲基蓝的降解活性, 发现2种化合物对于亚甲基蓝均表现出显著的光降解活性, 并对它们的催化机理进行了讨论.     

基于乳酸衍生物的螺旋手性配位聚合物的合成与荧光性质

在水热条件下,半刚性的乳酸衍生物(R)-(1-羧基乙氧基)苯甲酸[(R)-H₂CBA]和(S)-(1-羧基乙氧基)苯甲酸[(S)-H₂CBA]分别与辅助配体1,1'-(2,5-二甲基-1,4-亚苯基)双(1H-咪唑), 1,4-PBM和Zn(Ⅱ)反应,合成了一对包含螺旋链的三维超分子手性配位聚合物[Zn₂((R)-CBA)₂(1,4-PBM)₂]_n(1-D,CCDC:2010329)和[Zn₂((S)-CBA)₂ (1,4-PBM)₂]_n(1-L, CCDC:2010330),其结构和性能经IR, XRD, TGA和FL表征。结果表明：1-D结晶于单斜的P2₁手性空间群,晶胞参数a=8.9753(5)Å, b=18.2446(8)Å, c=15.1201(12)Å,β=90.935(6)°,V=2475.7(3)ų, Dc=1.373g·cm^-3, Z=2, Flack parameter=0.022(6); 作为对映体,1-L也结晶于单斜的P2₁手性空间群,晶胞参数a=9.0090(6)Å, b=18.2280(8)Å, c=15.1227(10)Å,β=90.935(6)°, V=2483.1(3) ų, Dc=1.369 g·cm^-3, Z=2,Flack parameter=0.060(7)。 1-D和1-L的初始分解温度为317℃;1-D在440 nm处有强发射峰。      

吡啶盐/咪唑盐调控钴萘基二膦酸配位聚合物的结构和性质

通过引入质子化的1,3-二(4-吡啶基)丙烷(1,3-dppH₂²⁺)和双(咪唑-1-甲基)苯(1,4-bixH₂²⁺)作为阳离子模板,采用水热反应,得到3种基于1,4-萘二膦酸(1,4-ndpaH₄)配体的钴萘二膦酸配位聚合物：(1,3-dppH₂)₂[Co₄(1,4-ndpa)(1,4-ndpaH)₂(1,4-ndpaH₂)]·6H₂O (1)、(1,4-bixH₂)_0.5[Co(1,4-ndpaH)](2)和(1,4-bixH₂)_0.5[Co₂(1,4-ndpaH)(1,4-ndpaH₂)(H₂O)₂](3)。对配合物1～3分别进行了元素分析、红外光谱、单晶X射线衍射、...     

辅助配体调控的荧光Cd-MOFs: 乙酰丙酮的荧光增强和Cr(Ⅵ)的荧光猝灭

将柔性苄氨基三羧酸配体5-(3-羧基-4-甲氧基苄氨基)间苯二甲酸(H₃L)与硝酸镉和不同含氮配体在溶剂热条件下反应, 制得了配合物{[Cd(HL)(bpea)·H₂O]·H₂O·DMF}_n(1)、 {[Cd(HL)(bpp)·H₂O]·2H₂O·DMF}_n(2)和 {[Cd(HL)(dmbpy)]·DMF}_n(3)[bpea=bis(4-pyridyl)ethane; bpp=1,3-bis(4-pyridyl)propane; dmbpy=5,5′-dimethyl-2,2′-bipyridine]. 3个配合物分别表现出有趣的2D→2D穿插结构和一维带状结构. 荧光性质测试结果表明, 所有配合物的荧光均可被Cr₂O₇^2?猝灭, 而在乙酰丙酮的DMF溶液中, 只有配合物1表现出明显的荧光增强. 羧酸配体的柔性、 含氮配体的类型和结构可以调控配合物的结构和荧光性能.     

系列Sm3+配合物的合成、结构及光物理性能

采用水热方法合成了4种Sm³⁺配合物, 即{[SmZn(2,5-pdc)₂(tp)_0.5(H₂O)]·2H₂O}_n(1), [Sm₂Zn₂(C₆H₅COO)₁₀(Imh)₂(H₂O)₂](2), {[Sm₂(NO₂C₆H₄COO)₆(H₂O)₄]·H₂O}_n(3)和{[SmN(CH₂COO)₃(H₂O)₂]·H₂O}_n(4)[2,5-pdc=2,5-吡啶二羧酸根, tp=对苯二甲酸根, C₆H₅COO=苯甲酸根, Imh=咪唑, NO₂C₆H₄COO=对硝基苯甲酸根, N(CH₂COO)₃=氨三乙酸根]. 通过单晶X射线衍射确定了其晶体结构. 在室温下测定了其红外光谱、 紫外-可见-近红外光谱以及在近红外区和可见区的发射光谱. 结果表明, 4种配合物在近红外区或可见区均出现Sm³⁺离子的特征发射. 这是形成配合物后, Zn-配体部分和配体对Sm³⁺离子发光的敏化作用所致. 此外, 讨论了不同有机配体或d过渡金属离子对Sm³⁺离子发光的影响, 并分析了配合物中Sm³⁺离子的近红外发射带位移、 劈裂和加宽的原因.     

锌(Ⅱ)配合物的超分子设计及对甲醇蒸气的吸附性能

采用饱和蒸气扩散技术, 将2,4-二羟基苯甲醛缩异烟酰腙(H₂dhbi)配体分别与Zn(ClO₄)₂·6H₂O和Zn(NO₃)₂·6H₂O进行配位作用, 得到2种不同配位模式的金属-有机框架材料[(dhbi)₂Zn₂·8H₂O]_n(1)和{[(dhbi)₂(H₂O)₂Zn₂]·4DMF]}_n(2). 利用X射线单晶衍射、 热分析技术(TG-DTA)和X射线粉末衍射(PXRD)等方法进行了结构表征. 进一步将配位聚合物1和2用于对甲醇分子的吸附性能研究, 结果表明, 化合物1是一种理想的微孔材料, 其对甲醇分子的吸附能力为化合物2的近5倍, 采用PLATON对材料的孔隙体积进行计算得到化合物1和2的孔隙率分别为38.2%和5.5%.     

{(Me2NH2)2[Fe2(ox)2Cl4]•H2O} n (ox=oxalate)中客体水分子诱导的介电弛豫行为

以双齿配位的草酸根为配体和FeCl₃反应得到了化合物{(Me₂NH₂)₂[Fe₂(ox)₂Cl₄]•H₂O} _n (ox=oxalate) ( 1•H₂O). 在真空和加热的条件下, 1•H₂O脱水发生单晶到单晶的转变, 得到了化合物{(Me₂NH₂)₂[Fe₂(ox)₂Cl₄]} _n ( 1). 磁性研究表明客体水分子存在与否对化合物磁相互作用没有明显影响. 介电性质研究表明客体水分子的存在可影响化合物中客体胺和氢原子的动态弛豫过程. 化合物 1•H₂O在250 K, 80 K和50 K呈现三个介电弛豫过程, 而化合物 1仅在80 K表现出单一弛豫过程.     

A Novel 3D CdⅡ-CP Based on a Bi-functional（N-/O-Sites） Triazole-modified Carboxyl Ligand: Structure,Topology and Photoluminescence

With triazole-modified derivative as link,one new framework[Cd₅(μ₅-HL^2-)₂(μ₄-L^3-)₂（H₂O）₁₀]·2H₂O(1,H₃L=2-（1,2,4-triazol-1-yl）benzene-1,3,5-tricarboxylic acid) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction,powder X-ray diffraction and elemental analysis.Complex 1exhibits a 3D （3,4,6）-connected net cross-linked by binuclear[Cd₂     

具有螺旋结构的金属镍有机-无机配位聚合物的合成及表征

在水热体系中合成了3个中心金属为镍离子, 以六配位扭曲八面体构型形成的具有螺旋结构的配位聚合物{[Ni₂L₂(bib)₂·2H₂O]·5H₂O}_n(1), [Ni₂L₂(bpy)]_n(2)和{[Ni₂L₂(bibpip)₂·2H₂O]·6H₂O}_n(3)[H₂L=4,4'-三苯胺二甲酸; bib=1,3-二(咪唑基)苯; bpy=4,4-联吡啶; bibpip=1,4-二(4-咪唑苄基)哌嗪]. 通过单晶及粉末X射线衍射、 红外光谱、 元素分析和热重分析对这3种化合物进行了表征. 结果表明, 化合物1属于单斜晶系, C2/c空间群, 其骨架为具有{4²·6⁵·8}拓扑结构的二维层结构; 化合物2属于斜方晶系, Fdd2空间群, 其骨架为具有{4⁸·5⁴·6³}拓扑结构的三维超分子网络; 化合物3属于三斜晶系, P\begin{array}{c}\bar{1}\end{array}空间群, 为1个五重穿插的三维超分子网络, 其骨架具有{4⁴·6²}拓扑结构.     

具有四连接网络的单一手性螺旋配位聚合物的合成与结构表征

在水热反应条件下,使用乳酸衍生物[(R)-H2CBA和(S)-H2CBA]和辅助配体1,4-DIB与Ni2+组合,制备出一对具有dia拓扑网络的单一手性框架材料[Ni2((R)-CBA)2(1,4-DIB)3(H2O)2]·x H2O(1-D)和[Ni2((S)-CBA)2(1,4-DIB)3(H2O)2]·x H2O(1-L).配合物1-D和1-L具有2种由1,4-DIB与Ni2+组构建而成的螺旋链以及二重穿插的结构特征.此外,对上述配合物进行了粉末X射线衍射、热失重和圆二色谱测试并对结果进行了分析.     

Two Pairs of Homochiral Coordination Polymers with Helices Based on Semi‐rigid Lactic Acid Ligands

Utilizing semirigid lactic acid derivatives (R)‐H₂CBA and (S)‐H₂CBA as chiral ligands, two pair of homochiral coordination polymers formulated as [Zn((R)‐CBA)(1,4‐DIB)] · H₂O ( 1 ‐ D ), [Zn((S)‐CBA)(1,4‐DIB)] · H₂O ( 1 ‐ L ), [Co((R)‐CBA)(1,4‐DIB)] · H₂O ( 2 ‐ D ) and [Co((S)‐CBA)(1,4‐DIB)] · H₂O ( 2 ‐ L ) were prepared under solvothermal reaction condition. Single X‐ray diffraction study reveals that all the complexes are comprised of three kinds of helical chains, which are constructed by corresponding metal ions, CBA^2– ligands, and/or 1,4‐DIB ligands. Moreover, some physical characteristics, such as PXRD, thermal stabilities, solid‐state circular dichroism (CD), luminescent and magnetic properties are also investigated.     

Two Heteroligand Cd(II)-coordination Polymers: Crystal Structures and Anti-Lung Cancer Activity Evaluation

Russian Journal of Coordination Chemistry - Two new Cd(II) containing coordination polymers, namely {[Cd(Dib)(1,4-Ndc)] · H2O}n (I, Dib = 1,4-di(1H-imidazol-1-yl)butane, 1,4-H2Ndc =...     

Chiral monomeric and homochiral dimeric copper(II) complexes of a new chiral ligand, N-(1,2-bis(2-pyridyl)ethyl)pyridine-2-carboxamide: an example of molecular self-recognition

Reaction of Cu(ClO(4))(2) x 6H(2)O with a racemic mixture of the novel chiral ligand N-(1,2-bis(2-pyridyl)ethyl)pyridine-2-carboxamide (PEAH) affords only the homochiral dimeric copper(II) complexes [Cu(2)((R)()PEA)(2)](ClO(4))(2) and [Cu(2)((S)()PEA)(2)](ClO(4))(2) in a 1:1 ratio. The phenomenon of molecular self-recognition is also observed when a racemic mixture of the monomeric copper(II) complex [Cu((R(S))()PEA)(Cl)(H(2)O)] is converted into the homochiral dimeric species [Cu(2)((R(S))()PEA)(2)](ClO(4))(2) via reaction with Ag(+) ion. This is the first report of direct conversion of a racemic mixture of a chiral monomeric copper(II) complex to a mixture of the homochiral dimers.     

Mono- and dinuclear complexes of chiral tri- and tetradentate Schiff-base ligands derived from 1,1'-binaphthyl-2,2'-diamine

The synthesis and characterization of the bis(bidentate) Schiff-base ligand [(R)-2] formed by the condensation reaction of (R)-1,1'-binaphthyl-2,2'-diamine [(R)-BINAM] with pyridine-2-carboxaldehyde is presented. The coordination chemistry of (R)-2 with Ni(ClO(4))(2).6H(2)O, Co(ClO(4))(2).6H(2)O, CuCl(2), and CuSO(4) has been investigated. Reaction of (R)-2 with the first two metal salts leads to complexes of the type [M((R)-4)(2)](ClO(4))(2) (M = Ni(II), Co(II)), where (R)-4 is a tridentate ligand resulting from the hydrolytic cleavage of one of the pyridyl groups from (R)-2. Both complexes were characterized by X-ray crystallography, which showed that the Lambda absolute configuration of the metal center is favored in both cases. (1)H NMR spectroscopy suggests that the high diastereoselectivity of Lambda-[Co((R)-4)(2)](ClO(4))(2) is maintained in solution. The reaction of (R)-2 with CuCl(2) leads to the dinuclear complex [Cu(2)((R)-2)Cl(4)], which has a [Cu(2)(mu(2)-Cl(2))] core. The reaction of CuSO(4) with (R)-2 gives a dimeric complex, [Cu((R)-4)SO(4)](2), which features a [Cu(2)(mu(2)-(SO(4))(2))] core. This complex can be prepared directly by the reaction of (R)-BINAM with pyridine-2-carboxaldehyde and CuSO(4). The use of rac-BINAM in this synthetic procedure leads to the heterochiral dimer [Cu(2)((R)-4)((S)-4)(SO(4))(2)]; that is, the ligands undergo a self-sorting (self/nonself discrimination) process based on chirality. The reaction of rac-BINAM, pyridine-2-carboxaldehyde, and Co(ClO(4))(2).6H(2)O proceeds via a homochiral self-sorting pathway to produce a racemic mixture of [Co((R)-4)(2)](2+) and [Co((S)-4)(2)](2+). The variable-temperature magnetic susceptibilities of the bimetallic complexes [Cu(2)((R)-2)Cl(4)], [Cu((R)-4)(mu(2)-SO(4))](2), and [Cu(2)((R)-4)((S)-4)(mu(2)-SO(4))(2)] all show weak antiferromagnetic coupling with J = -1.0, -0.40, and -0.67 cm(-)(1), respectively.     

Syntheses, structures and luminescent properties of new lanthanide-based coordination polymers based on 1,4-benzenedicarboxylate (bdc)

Reaction of 1,4-benzenedicarboxylic acid (1,4-H(2)BDC) with EuCl(3).6H(2)O in MeOH in the presence of Et(3)N and MeCN gives a mixture of the 3-D metal-organic-framework (MOF) materials [Eu(2)(1,4-BDC)(3)(MeOH)(4)].8MeOH () and 2-D [Eu(1,4-BDC)(MeOH)(4)].Cl.MeOH.0.25H(2)O (). Similar reactions afforded the isomorphous Gd () and Tb () analogs of . Reaction of 1,4-H(2)BDC with Ln(NO(3))(3).6H(2)O under similar conditions gave [Ln(BDC)NO(3)(MeOH)(2)].MeCN.H(2)O (Ln = Eu () and Gd ()), which have 2-D framework structures. The structures of were determined by single crystal X-ray crystallographic studies and the luminescence properties of and in DMF solution were determined.     

两类hcb网络构筑的三维柱层结构Ni(Ⅱ)基金属-有机框架化合物

在溶剂热合成体系中,5-羟基间苯二甲酸(H 2HIPA)和1,4-二(1氢-咪唑-1-基)苯(1,4-DIB)与Ni(Ⅱ)离子反应得到一个结构新颖的化合物Ni[(HIPA)(1,4-DIB)](1,CCDC:2034033)。单晶结构分析揭示化合物1结晶于单斜的P21/c空间群。HIPA 2-和1,4-DIB分别被Ni(Ⅱ)离子连接在一起形成了两种具有hcb网络的二维结构,也就是Ni-HIPA和Ni-1,4-DIB层。这两类二维的层状结构进一步形成(3,6)-连接网络特征的三维柱层式框架。此外,在紫外-可见吸收光谱上化合物1在200-450和520-750nm范围内有两个强的吸收峰,依据Kubelka-Munk(KM)方法其带隙宽度为2.1V,具有半导体特征。化合物1的相纯度和热稳定性也通过粉末衍射和热失重分析测试予以确认。     

Fluorescent metal-organic polymers of zinc and cadmium from hydrothermal in situ acylation reaction

A series of metal-organic complexes based on d(10) metals and the ligand H(4)bbh (H(4)bbh = benzene-1, 2, 4, 5-biformhydrazide), formed through hydrothermal in situ acylate reaction of H(4)bta (H(4)bta = benzene-1, 2, 4, 5-tetracarboxylic acid) with hydrazine hydrate (N(2)H(4)·H(2)O), have been prepared and structurally characterized by single-crystal X-ray diffraction. Compounds [Zn(μ(2)-H(2)bbh)(phen)(H(2)O)](2) (1) (phen = 1, 10-phenanthroline) and [Zn(μ(2)-H(2)bbh)(2, 2'-bpy)](2) (2) (2, 2'-bpy = 2, 2'-bipyridine) are both dinuclear complexes in which bridging ligands H(2)bbh(2-) display different μ(2)- coordination modes. [Zn(μ(2)-H(2)bbh)(1/2)(μ(2)-H(2)bbh)(1/2)(H(2)O)](n) (3) exhibits a two-dimensional (2-D) layer structure containing simultaneously two kinds of different coordination modes of H(2)bbh(2-): μ(2)-bidentate and μ(4)-tetradentate. [Cd(μ(3)-H(2)bbh)(phen)](n) (4) consists of one-dimensional (1-D) double-metal chains. The crystal structures of these compounds are stabilized by hydrogen bonds and π···π interactions, forming three-dimensional supramolecular networks. All of the compounds were characterized by IR, UV-vis spectra and elemental analysis and they show good fluorescence properties in the solid state at room temperature. In order to understand the emission mechanism, we carried out TDDFT calculations on the excited electronic states of compound 2.     

A chiral porous 3D metal-organic framework with an unprecedented 4-connected network topology

A novel homochiral 3D metal-organic framework [CdL2(H2O)2][ClO4]2.2DMF.3EtOH.5/3H2O, 1, (L =(R)-6,6-dichloro-2,2-diethoxy-1,1-binaphthyl-4,4-bipyridine) exhibits an unprecedented 4-connected network topology owing to the cis- configuration of the Cd coordination and possesses permanent porosity as demonstrated by TGA, XRPD, and CO2 adsorption isotherm studies.     

Rational design of MOFs constructed from modified aromatic amino acids

Three Phe and Tyr derivatives, 2-amino-3-(4-aminophenyl)-propionic acid (AAP), 3E-[5-(2-amino-2-carboxyethyl)-2-methoxyphenyl]-acrylic acid (AMPA) and 3-(4-aminophenyl)-2-(carboxymethyl-amino)-propionic acid (ACP) have been chosen as the ligands to construct four kinds of novel metal-organic frameworks (MOFs) (five structures). These structures are, [Cd(II){(R)-AAP}(Py)(H(2)O)](ClO(4)), (R)-1; [Cd(II){(S)-AAP}(H(2)O)(2)](ClO(4)), (S)-2; [Zn(2) (II){(R,S)-AMPA}(H(2)O)], (R,S)-3; [Zn(2) (II){(R)-ACP}(Py)(3)](ClO(4))(2), (R)-4; and the inversion twin of (R)-1. Rational design to adjust the "depth" and the "width" of ligands can mediate the size and the shape of the grids of these 2D layers. Additionally, among these compounds, three pure chiral coordination polymers are obtained, owing to the inducement of chirality by the modified amino acids. This property makes them potential NLO materials.