微孔镧系配位聚合物

微孔配位聚合物与通常的微孔无机材料相比, 具有非常明显的优势. 而镧系离子特殊的光学和磁学性质, 更使得微孔镧系配位聚合物的研究成为热点. 本文简要地报道了微孔镧系配位聚合物的研究现状, 对一些微孔镧系配位聚合物的结构特点进行了描述, 讨论了影响微孔配位聚合物形成的主要因素. 一般来说, 线型配体往往能很好地将金属离子连接起来, 得到理想的微孔镧系配位聚合物; 选择合适的第二配体, 有利于构筑结构新颖的微孔镧系配位聚合物; 镧系收缩对能否形成微孔配位聚合物的影响并不明显, 只是轻稀土离子往往倾向于多结合一些小分子配体来满足更高的配位数.     

2-(1H-1，2，4-三氮唑)乙酸-稀土配合物的合成与结构

利用柔性含氮配体羧酸2-(1H-1,2,4-三氮唑)乙酸(HL)与稀土氧化物在水热条件下反应得到了2个稀土配位聚合物 [Gd(L)₃H₂O]_n(1)和[Nd(L)₃H₂O]_n(2)。利用元素分析、红外光谱、X射线单晶衍射结构分析等方法对其进行了表征。晶体结构表明2个配合物晶体同属三斜晶系,空间群P1,具有一维链状结构。     

Synthesis of Lanthanide Coordination Polymers with Benzophenone-4,4-dicarboxylate: Effect of Lanthanide Contraction on Structures

Introduction Recently, the coordination polymers based on dicar-boxylic acid have been studied extensively for their importance as promising materials.1-7 So the rational design and synthesis of novel coordination polymers with useful functions attract considerable attention. As well known, the design of extended structure with po-tential applications can be realized by starting with connecting ligands capable of binding metal centers strongly and predictably to afford the structures with expe…     

Triboluminescence of Lanthanide Coordination Polymers with Face-to-Face Arranged Substituents

Luminescence upon the grinding of solid materials (triboluminescence, TL) has long been a puzzling phenomenon in natural science and has also attracted attention because of its broad application in optics. It has been generally considered that the TL spectra exhibit similar profiles as those of photoluminescence (PL), although they occur from distinct stimuli. Herein, we describe for the first time a large spectral difference between these two physical phenomena using lanthanide^III coordination polymers with efficient TL and PL properties. They are composed of emission centers (Tb^III and Eu^III ions), antenna (hexafluoroacetylacetonate=hfa), and bridging ligands (2,5-bis(diphenylphosphoryl)furan=dpf). The emission color upon grinding (yellow TL) is clearly different from that upon UV irradiation (reddish-orange PL) in Tb^III/Eu^III-mixed coordination polymers [Tb,Eu(hfa)₃(dpf)]_n (Tb/Eu=1). The results directly indicate the discrete excitation processes of PL and TL.     

The Effect of Auxiliary Nitrogenated Linkers on the Design of New Cadmium-Based Coordination Polymers as Sensors for the Detection of Explosive Materials

Three new cadmium-based coordination polymers, denoted [Cd(hfipbb)(4,4’-bipy)] ( CdPF-1 ), [Cd(hfipbb)(2,2’-bipy)] ( CdPF-2 ), and [Cd(hfipbb)(1,10-phen)] ( CdPF-3 ), have been hydrothermally synthesized by using the well-known V-shaped organic linker 4,4’-(hexafluoroisopropylidene)bis(benzoic acid) (H₂hfipbb), together with different nitrogenated auxiliary linkers. Considering the d¹⁰ configuration of the transition metal selected, the luminescent properties for these CdPF-n materials were explored, finding that materials CdPF-2 and CdPF-3 act as excellent sensors in the detection of explosive nitro aromatic compounds. The photoluminescence properties of CdPF-2 and CdPF-3 revealed that significant and sensitive fluorescence quenching was observed toward NP (nitrophenol) for CdPF-2 and PA (picric acid) for CdPF-3 in MeOH suspensions.     

Statistic Replacement of Lanthanide Ions in Bis-salicylatoborate Coordination Polymers for the Deliberate Control of the Luminescence Chromaticity

Based on the strand-like coordination polymer (CP) type ¹_∞[Ln(BSB)₃(py)₂], [BSB]⁻=bis-salicylatoborate anion, mixed Eu/Tb-containing compounds of the constitution ¹ _∞ [Eu_xTb_1−x(BSB)₃(py)₂] were synthesised ionothermally for a phase width of (x=0.25–0.75) and characterized regarding structure and optical properties. Previously, known only for other lanthanides, the mixed 1D−Eu/Tb-CPs show excellent options for statistic replacement of the Ln-cations during synthesis yielding solid solutions. The products are highly luminescent, with the chromaticity being a direct function of the amount of the respective Ln-ions. Corresponding to an overall addition of emission intensities, the green Tb³⁺ emission and the red Eu³⁺ emission allow for a chromaticity control that also includes yellow emission. Control of the luminescence colour renders them suitable examples of the versatility of statistic replacement of metal ions in coordination chemistry. In addition, crystallization of [EMIm]₂[YCl₅(py)] illuminates possible other products of the ionothermal reactions of [EMIm][BSB] with LnCl₃ constituted by components not being part of the main CPs.     

Lanthanide Coordination Polymers Constructed from Infinite Rod‐Shaped Secondary Building Units and Flexible Ligands

Three lanthanide coordination polymers constructed from infinite rod‐shaped secondary building units (SBUs), [Nd₂(H₂O)₂(cis‐chdc)₂(trans‐chdc)]?2H₂O ( 1 ), Nd₂(H₂O)₄(trans‐chdc)₃ ( 2 ), and [Sm₂(H₂O)₂(cis‐chdc)(trans‐chdc)₂]?4H₂O ( 3 ) (chdcH₂=1,4‐cyclohexanedicarboxylic acid), were hydrothermally synthesized and structurally characterized. The structures of 1 – 3 are modulated by different ratios of the cis and trans configurations of chdc^2? ligands, which was achieved by temperature control in the hydrothermal reactions. Crystal‐structure analysis revealed that 1 is a four‐connected pcu‐type rod packing network built from cross‐linking of rod‐shaped neodymium–oxygen SBUs by cis‐ and trans‐chdc^2? ligands in a 2:1 ratio, 2 displays a complicated six‐connected hex‐type rod packing structure built by connection of rod‐shaped neodymium–oxygen SBUs and trans‐chdc^2? ligands, and 3 features an unprecedented five‐connected rod packing pattern constructed from rod‐shaped samarium–oxygen SBUs and cis‐ and trans‐chdc^2? ligands in a 1:2 ratio.     

An Insight into nd10 Metal Cyanide-based Coordination Polymers Through ab-initio Calculations: Electronic Properties and Optical Response

Semiconductors are essential for modern life since they are the basis of many current technologies that are related to better living standards. Some of them, characterized by the periodic assembling of metal cyanides with filled d-shell (nd¹⁰) constitute an interesting series of cyanide-based coordination polymers with physical properties such like anomalous anisotropic thermal expansion and quantum confinement effects related to the polymer's width that can be exploited for technological applications. Herein, the electronic structure of nd¹⁰ metal cyanide-based systems were studied both experimentally and through Density Functional Theory. The band gap found for one-dimensional (1D) −M−C≡N− (M=Cu, Ag, Au) and tetrahedral M−(C≡N)₂ (M=Zn, Cd, Hg) systems can be attributed to Laporte-allowed π π* (Metal to Ligand Charge Transfer mechanism) combined with metal center (d s,p) electronic transitions. Aurophilic bonding was found on the AuCN structure, and a new forbidden electronic transition associated to its band gap is reported. Computed effective and reduced masses from carriers revealed that carrier mobility and quantum confinement effects are greater in 1D systems.     

Self-Assembly of 1D Double-Chain and 3D Diamondoid Networks of Lanthanide Coordination Polymers through In Situ-Generated Ligands: High-Pressure CO2 Adsorption and Photoluminescence Properties

Two new lanthanide-based coordination polymers, [Sm₂(bzz)(ben)₆(H₂O)₃]·0.5H₂O (1) and [Eu(bbz)(ben)₃] (2), were synthesized and characterized. The described products were formed from in situ-generated benzoate (ben) and N’-benzoylbenzohydrazide (bbz) ligands, which were the products of transformation of originally added benzhydrazide (bzz) under hydrothermal conditions. Compound 1 exhibits a one-dimensional (1D) double-chain structure built up from the connection of the central Sm³⁺ ions with a mixture of bzz and ben ligands. On the other hand, 2 features a 3D network with a 4-connected (6⁶) dia topology constructed from dinuclear [Eu₂(ben)₆] secondary building units and bbz linkers. High-pressure CO₂ sorption studies of activated 1 show that maximum uptake increases to exceptionally high values of 376.7 cm³ g⁻¹ (42.5 wt%) under a pressure of 50 bar at 298 K with good recyclability. Meanwhile, 2 shows a typical red emission in the solid state at room temperature with the decay lifetime of 1.2 ms.     

A New Hybrid Cmpo/Nopopo Ligand: Synthesis and Selected Lanthanide Coordination Chemistry

Abstract

A two-step synthesis for 2,6-bis[(diphenyl)-N,N-diethylcarbamoylmethylphosphine oxide]pyridine N-oxide (3) from 2,6-bis[(diphenylphosphinoyl)methyl]pyridine is reported along with coordination chemistry with Dy(III) and Yb(III). Crystal structure determinations for the ligand 3_S,S and 1:1 complexes [Dy(3_R,S )(NO₃)₃]·(Me₂CO) and [Yb(3_R,S )(NO₃)₃]·(Me₂CO) are described. In these complexes, the pentafunctional ligand 3 coordinates in a tridentate NOPOPO chelate mode.     

Lanthanide Complexes of Azidophenacyl‐DO3A as New Synthons for Click Chemistry and the Synthesis of Heterometallic Lanthanide Arrays

Lanthanide complexes of azidophenacyl DO3A are effective substrates for click reactions with ethyne derivatives, giving rise to aryl triazole appended lanthanide complexes, in which the aryl triazole acts as an effective sensitising chromophore for lanthanide luminescence. They also undergo click chemistry with propargylDO3A derivatives, giving rise to heterometallic complexes.     

两个一维配位聚合物的合成、晶体结构、电化学及光学性质

合成了2个新的Robson大环配位聚合物{[Mn₂L¹(1,4-bix)₂](ClO₄)₂·5H₂O·DMF}_n(1)和{[Cu₂L²(1,4-bix)](ClO₄)₂}_n(2)(H₂L¹和H₂L²分别为1,3-丙二胺与2,6-二甲酰基-4-氟苯酚和2,6-二甲酰基-4-氯苯酚通过[2+2]缩合的产物)。2个配合物通过1,4-二(1,2,4-三唑-1-甲基)苯(1,4-bix)桥连大环单元形成一维链状结构。配合物的HOMO-LUMO能带间隙通过循环伏安法、紫外-可见漫反射光谱进行了测定,结果表明有较低的能带间隙。     

Synthesis,Structure, and Luminescent Properties of Lanthanide Coordination Polymers Based on 5‐Hydroxyisophthalate and Phen Ligands

Three lanthanide coordination polymers incorporating 5‐hydroxyisophthalate ( L ) and phen ligands, [Eu( L )(phen)]_n ( 1 ) and [Ln( L )(phen)₂]_n [Ln = Sm ( 2 ) and Pr ( 3 )], were synthesized. X‐ray structural analysis reveals that 1 features a (3,6)‐connected 3D rtl topology. Complexes 2 and 3 are isostructural and have 2D sheets with 6³ topology. Comparison of the structural differences between 1 and 2 (or 3 ) suggests that the different metal sources play an important role in the formation of such coordination networks. Compounds 1 and 2 show photoluminescence and their emission properties are closely related to their corresponding central Ln^III atoms.     

两个一维配位聚合物的合成、晶体结构、电化学及光学性质

合成了2个新的Robson大环配位聚合物{[Mn₂L¹（1,4-bix）₂]（ClO₄）₂·5H₂O·DMF}_n （1）和{[Cu₂L²（1,4-bix）]（ClO₄）₂}_n （2）（H₂L₁和H₂L₂分别为1,3-丙二胺与2,6-二甲酰基-4-氟苯酚和2,6-二甲酰基-4-氯苯酚通过[2+2]缩合的产物）。2个配合物通过1,4-二（1,2,4-三唑-1-甲基）苯（1,4-bix）桥连大环单元形成一维链状结构。配合物的HOMO-LUMO能带间隙通过循环伏安法、紫外-可见漫反射光谱进行了测定,结果表明有较低的能带间隙。     

一维交替链状稀土配位聚合物[Er(dpa)(pya)(H2O)]n和[Nd2(pya)6(H2O)4]n的水热合成及结构表征

在水热条件下，稀土氧化物与2，2′-联苯二甲酸及异烟酸反应得到了两个新颖的一维交替链状配位聚合物[Er(dpa)(pya)(H₂O)]_n和[Nd₂(pya)₆(H₂O)₄]_n(H₂dpa=2，2′-联苯二甲酸；Hpya=异烟酸)。测定了它们的晶体结构，并进行了红外光谱和元素分析等 性质的表征。晶体结构测定表明这两个化合物同属单斜晶系，并具有相同的空间群P2₁/n， 晶体学参数分别为配合物1：a= 0.8830(3) nm，b=1.058 5(3) nm，c=2.089 1(6) nm，β=98.429(4)°，D_c=1.883g·cm^-3， V=1.931 4(10) nm³，Z=4； 配合物2：a=0.968 9(4) nm，b=1.978 3(9) nm，c=1.164 2(6) nm，β=112.106(7)°，D_c=1.756 g·cm^-3，V=2.067 5(17) nm³，Z=4。     

M-Carboxylic Acid Induced Formation of New Coordination Polymers for Efficient Photocatalytic Degradation of Ciprofloxacin

Four new 2–3D materials were designed and synthesized by hydrothermal methods, namely, {[(L1·Cu·2H₂O) (4,4-bipy)_0.5] (β-Mo₈O₂₆)_0.5·H₂O} (1), {[(L1·Cu)₂·(4,4-bipy)] (Mo₅O₁₆)} (2), {Co(L1)₂}_n (3), and {[(L1)₂][β-Mo₈O₂₆]_0.5·5H₂O} (4). [L1=5-(4-aminopyridine) isophthalic acid]. The degradation of ciprofloxacin (CIP) in water by compounds 1–4 was studied under visible light. The experimental results show that compounds 1–4 have obvious photocatalytic degradation effect on CIP. In addition, for compound 1, the effects of temperature, pH, and adsorbent dosage on photocatalytic performance were also investigated. The stability of compound 1 was observed by a cycle experiment, indicating that there was no significant change after three cycles of CIP degradation.     

Luminescent Europium(III) Coordination Zippers Linked with Thiophene‐Based Bridges

Novel Eu^III coordination polymers [Eu(hfa)₃(dpt)]_n (dpt: 2,5‐bis(diphenylphosphoryl)thiophene) and [Eu(hfa)₃(dpedot)]_n (dpedot: 2,5‐bis(diphenylphosphoryl)ethylenedioxythiophene) with hydrogen‐bonded zipper structures are reported. The coordination polymers are composed of Eu^III ions, hexafluoroacetylacetonato ligands, and thiophene‐based phosphine oxide bridges. The zig‐zag orientation of single polymer chains induced the formation of densely packed coordination structures with multiple intermolecular interactions, resulting in thermal stability above 300 °C. They exhibit a high intrinsic emission quantum yield (ca. 80 %) due to their asymmetrical and low‐vibrational coordination structures around Eu^III ions. Furthermore, the characteristic alternative orientation of substituents also contributes to the dramatically high ligand‐to‐metal energy transfer efficiencies of up to 80 % in the solid state.     

光致变色液晶高分子信息存储材料研究进展

本文系统阐述了光致变色液晶高分子的研究概况、光信息存储机理以及信息存储应用方面的研究进展。     

对苯二甲酸及双酚A衍生物构筑的二维镉配位聚合物的合成、结构及性质(英文)

以4,4-二(4-羟乙基苯并咪唑基苯基)丙烷(L1),4,4-二(4-羟乙基咪唑基苯基)丙烷(L2)为原料,通过水热法得到2个二维结构的配位聚合物{[Cd(L1)(bdc)H2O]·2DMA}n(1),[Cd(L2)(bdc)H2O]n(2)(H2bdc=对苯二甲酸,DMA=N,N-二甲基乙酰胺),通过X-射线单晶洐射、热重以及红外光谱对其进行了表征。结果显示晶体1为单斜晶系,P2/c空间群。晶体2为单斜晶系,C2/c空间群。配合物2为2D→2D穿插结构。热重分析表明配合物1和2分别在343和325℃时分解。