Crystal Structure,Fluorescence and Thermal Stability Properties of a Dinuclear Copper(Ⅱ) Complex[Cu_2(L)_2(phen)_2]-5H_2O(H_2L = Bicycle[2.2.1]hept-2-en-5,6-dicarboxylic acid)

A new dinuclear copper（II） complex [Cu2（L）2（phen）2]·5H2O （1） with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid （H2L） and 1,10-phenanthroline （phen） as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a = 17.925（4）, b = 19.908（4）, c = 11.235（2） A, β = 97.65（3）°, V= 3973.4（14） A3, Dc = 1.552 g/cm^3, Z = 8, F（000） = 1910, the final GOOF = 1.056, R= 0.0519 and wR= 0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by twoμ2-η1 ：η0-3-carboxylate groups of L^2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 rim. The TG analysis shows that I is stable below 143 ℃.

基于涤棉混纺织物的荧光碳点对Cr(Ⅵ)和Hg(Ⅱ)的检测

该文以废弃涤棉混纺织物为碳源,分别在乙二醇和硫酸溶液中通过溶剂热法合成了两种荧光碳点,实现了对溶液中Cr(Ⅵ)和Hg(Ⅱ)的检测。通过透射电镜与红外光谱表征了碳点的形貌与组成,并基于紫外吸收光谱和荧光光谱分析了碳点的电子跃迁形式及发光类型。在乙二醇体系中制得的碳点(ETCCDs)能够选择性检测Cr(Ⅵ),检出限为0.093 mg/L,其检测机理为荧光内滤效应;硫酸体系中制备的碳点(WTCCDs)能够选择性检测Hg(Ⅱ),检出限为0.018µmol/L,检测机理为能量转移。对实际水样中的Cr(Ⅵ)和Hg(Ⅱ)进行检测,验证了上述两种碳点的实用性。基于涤棉混纺织物制备的荧光碳点不仅实现了对两种重金属离子的检测,同时也为废旧纺织物的再生利用提供了借鉴意义。

Syntheses,Crystal Structures and Fluorescence Properties of Two Mononuclear Copper(Ⅱ) Compounds

Two new compounds,1（[Cu（IDB_）2]Cl_2·2CH_3CH_2OH·2H_2O（IDB = N,N-di（2-benzimidazolylmethyl）imine]） and 2（[Cu（EDTB）]·2[C_6H_4（OH）COO]·6H_2O（EDTB = N,N,N＇,N＇-tetrakis-[（2-benzimidazolyl）methyl]-1,2-ethanediamine]）,have been synthesized and their crystal structures were determined by single-crystal X-ray diffraction. Crystal 1 belongs to the triclinic system,space group P1 with a = 9.565（2）,b = 9.863（2）,c = 10.252（3） ？,α = 81.915,β = 88.330,γ = 87.347°,V = 956.28（40） ？3,Z = 1,F（000） = 427,D_c = 1.419 g/cm3,Mr = 817.27 and μ（MoKα） = 0.764 mm^（-1）. The final R indices（I 〉 2σ（I））： R = 0.0505,wR = 0.1417; R indices（all data）： R = 0.0591,wR = 0.1525. Crystal 2 is of triclinic system,space group P1 with a = 11.487（3）,b = 13.396（4）,c = 17.977（5） ？,α = 73.899（5）,β = 86.629（5）,γ = 65.018（4）°,V = 2403.8（12） ？3,Z = 2,F（000） = 1072,D3c = 1.417 g/cm,Mr = 1025.54,μ（MoKα） = 0.528 mm^（-1）. The final R indices（I 〉 2σ（I））： R = 0.0769,w R = 0.163 2; R indices（all data）： R = 0.0769,wR = 0.1632. The two compounds exhibit mononuclear structures. The copper（Ⅱ） atom of crystal 1 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand IDB to adopt a distorted octahedral coordination geometry. The copper（Ⅱ） atom of crystal 2 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand EDTB to show a distorted octahedral coordination geometry. Particularly,the two compounds exhibit fluorescent properties at room temperature in ethanol.

基于4-羟基间苯二甲酸和含氮杂环配体的Zn(Ⅱ)配合物的合成、晶体结构与荧光性质研究

在水热法条件下,4-羟基间苯二甲酸(H 2HPHA)和锌离子分别与1,2二(吡啶-4-基)乙烯(dpee)及4,4′-联吡啶(4,4′-bpy)反应得到了2个三维的配位聚合物[Zn(HPHA)(dpee)·(DMA)2]n(配合物1)和[Zn(HPHA)2(4,4′-bpy)2·DMA]n(配合物2)。用X射线单晶衍射测定了配合物的晶体结构,结果显示:配合物1属于单斜晶系,C2空间群,每个不对称单元由一个锌离子,一个4-羟基间苯二甲酸配体及一个1,2-二(吡啶-4-基)乙烯组成;配合物2属于单斜晶系,P12/c1空间群,每个不对称单元由两个锌离子,两个4-羟基间苯二甲酸配体及两个4,4′-联吡啶配体组成。荧光光谱分析结果表明:配合物1的最强激发峰和发射峰在分别在251和397 nm,配合物2的最强激发峰和发射峰分别在415和513 nm。热重分析表明两个配合物在室温下稳定。

溶剂热合成的锌(Ⅱ)MOF、晶体结构及其性质

在溶剂热的条件下,以1,3-双(咪唑)丙烷与均苯三酸作为混合配体,合成了一例锌(Ⅱ)的有机框架材料。即{[Zn_(2)(μ2-OH)L_(1)L_(2)]·DMAc·_(2)H_(2)O}n其中L_(1)为1,3-双(咪唑)丙烷,L2为1,3,5-苯三羧酸用表示,DMAc为N,N-二甲基乙酰胺。经X射线单晶衍射仪、红外光谱仪、粉末XRD、热重分析仪和元素分析仪表征,该MOF为3D→3D二重穿插三维骨架结构。此外,室温下固体荧光的测试结果表明:该MOF对苯胺有明显猝灭作用,所以MOF可以用在荧光分光光度计检测苯胺的传感器方面的应用。

Bis(1-(4-(dimethylamino)benzylidene)-4-phenylthiose micarbaznato)palladium(Ⅱ):Synthesis,Crystal Structure and Its Dual Fluorescence Property

The title compound bis（1-（4-（dimethylamino）benzylidene）-4-phenylthiosemicar-bazato）-palladium（Ⅱ）（PdL2） was obtained by reacting 1-（4-（dimethylamino）benzylidene）-4-phenyl-thiosemicarbazide with dichlorobis（benzonitrile）palladium（Ⅱ） in methanol,and its structure was characterized by single-crystal X-ray diffraction.The crystal of PdL2 was obtained in dimethyl-formamide（DMF） solvent with solvent molecules involved in the cell and crystallizes in the monoclinic system,space group C2 with a = 18.485（15）,b = 7.090（5）,c = 17.595（11） ,β = 121.21（3）o,V = 1972（2） 3,Z = 2,Mr = 847.40,Dc = 1.427 g/cm3,μ = 0.624 mm-1,F（000） = 880,R = 0.0607 and wR = 0.1358.The Pd atom adopts a distorted square planar coordination geometry with two Pd-N and two Pd-S bonds.The ligand loses a proton from its tautomeric thiol form and coordinates to the Pd atom via mercapto sulfur and the imine nitrogen atom,which binds to palladium as bidentate N,S-donors forming five-membered chelate rings.The complex formed hydrogen bonding interaction with solvent DMF molecules from the hydrogen of phenylamine to the oxygen of DMF and several intramolecular hydrogen bonds.Pd（Ⅱ） perturbed ligand π-π＊ transition and metal-to-ligand charge transfer（MLCT） transition are observed in its electronic absorption spectra.The complex exhibits intraligand 1π-π＊（IL） state and MLCT state dual fluorescent emissions in organic solvent at room temperature.

多功能Zn(Ⅱ)金属有机骨架荧光传感器检测苯甲醛、四环素、2,4,6-三硝基苯甲酸、氟啶胺、Cr_(2)O_(7)^(2-)和Fe^(3+)

成功制备了新型Zn(Ⅱ)金属有机骨架(MOF)[Zn_(2)(Hdepa)(dya)_(2)]_(n)(1)(H_(5)depa=2,2’,3,4’,5-二苯醚五羧酸,dya=2,2’-二吡啶胺)。单晶X射线衍射分析表明MOF 1由2个Zn^(2+)离子与1个Hdepa^(4-)离子和2个dya分子连接组成,通过氢键形成三维骨架。用粉末X射线衍射和IR表征了配合物1的相纯度。值得注意的是,配合物1具有优异的荧光特性和热稳定性,1的高灵敏度和选择性使其能够作为荧光传感器检测苯甲醛(BZH)、四环素(TC)、2,4,6-三硝基苯酚(TNP)、氟啶胺(Flu)、Cr_(2)O_(7)^(2-)和Fe^(3+)。此外,通过荧光寿命分析了Fe^(3+)、TC、BZH对MOF 1的荧光的猝灭过程,通过能量转移研究了Fe^(3+)、Cr_(2)O_(7)^(2-)、TNP、TC、BZH和Flu的荧光猝灭机理。

1-Pyrenecarboxaldehyde thiosemicarbazone:A novel fluorescent molecular sensor towards mercury(Ⅱ) ion

A novel and simple fluorescent molecular sensor,1-pyrenecarboxaldehyde thiosemicarbazone（Hpytsc）,was synthesized.Its higher sensitivity and selectivity to mercury（Ⅱ） ion were studied through absorption and emission channels.The UV-vis spectra show that the increasing mercury（Ⅱ） ion concentrations result in the decreasing absorption intensity.The fluorescence monomer emission of Hpytsc is enhanced upon binding mercury（Ⅱ） ion,which should be due to the 1：1 complex formation between Hpytsc and metal ion.

Synthesis, Crystal Structure and Fluorescent Property of a New One-dimensional Cadmium(Ⅱ) Coordination Polymer Based on 3,4-Thiophenedicarboxylic Acid and 1,10-Phenanthroline

A new cadmium（Ⅱ） polymer [Cd（tdc）（Phen）]n 1 （H2tdc = thiophene-3,4-dicar-boxylic acid, Phen = 1,10-phenanthroline） was synthesized under hydrothermal conditions. The compound crystallizes in the triclinic system, space group P , with a = 7.3150（10）, b = 10.3598（14）, c = 10.8784（15） , α = 82.2740（10）, β = 72.9730（10）, γ = 80.236（2）°, V = 773.68（18） 3, Z = 2, Mr = 462.74, Dc = 1.986 Mg/m3, μ = 1.58 mm-1, F（000） = 456, the final R = 0.0218 and wR = 0.0465 for 3361 observed reflections with Ⅰ 〉 2σ（Ⅰ）. The compound presents a one-dimensional （1-D） double-stranded structure and exhibits fluorescent emission at room temperature. Furthermore, infrared spectroscopy, elemental analyses, thermogravimetric analysis and powder X-ray diffraction properties of the compound are also investigated.

一维钴(Ⅱ)/镍(Ⅱ)配位聚合物的合成、结构、磁性及荧光传感性质

采用水热法合成了2个新的配位聚合物[Co(L)_(0.5)(1,4-bib)(H_(2)O)_(3)]n(1)和[Ni(L)_(0.5)(1,4-bib)(H_(2)O)_(3)]n(2)(H_(4)L=1,4-二(2,6-二甲基-3,5-二羧基吡啶基)苯,1,4-bib=1,4-双(1-咪唑基)苯),通过X射线单晶及粉末衍射、元素分析、红外光谱分析和热重分析对其结构进行表征。结构分析表明配合物1和2为异质同构,均为一维结构。通过变温磁化率测量发现,配合物1和2中的Co􀃭/Ni􀃭离子之间存在反铁磁相互作用。此外,配合物1可通过荧光猝灭法检测头孢克肟(CEF),配合物2可用来检测四环素(TET),该方法灵敏度高、选择性好,其检出限分别为0.86μmol·L^(-1)(CEF)和0.49μmol·L^(-1)(TET)。

Crystal Structure, Electrochemical and Fluorescent Properties of a New Copper(Ⅱ) Coordination Polymer with 2,3-Pyridinedi-carboxylic Acid

A new copper(Ⅱ)coordination polymer[Cu5(Hpt)5(H2O)2(2,3-PCA)2]n·12nH2O(1)has been successfully synthesized under hydrothermal conditions with copper hydroxide,3-(pyridin-2-yl)-1,2,4-triazole(Hpt)and 2,3-pyridinedi-carboxylic acid(2,3-PCA).The structure of the title compound was determined by X-ray diffraction analyses,elemental analyses and IR spectrum.The architecture of 1 consists of one-dimensional sandwich-like chains which are connected by extensive hydrogen bonding interactions.The solid-state photoluminescence displays an obvious emission band at 384 nm upon excitation at 340 nm.In addition,electrochemistry property has also been studied.

Hydrothermal Synthesis, Crystal Structure and Fluorescent Property of a Cd(Ⅱ) Complex Based on Biimidazole and Isonicotinate-N-oxide

A new complex [Cd（H2biim）2（H2O）2]·（ino）2·4H2O （H2biim = 2,2＇-biimidazole, ino = isonicotinate-N-oxide） has been prepared and characterized by single-crystal X-ray diffraction analysis, IR and fluorescence spectra analysis. The crystal is of triclinic system, space group P1 with a = 7.5380（6）, b = 8.0402（7）, c = 13.5094（11） , α = 104.269（1）, β = 93.604（1）, γ = 98.349（1）°, V = 780.93（11） 3, Mr = 765.00, Dc = 1.627 g/cm3, F（000） = 390, μ = 0.776 mm-1 and Z = 1. The final R = 0.0322 and wR = 0.0825 for 7038 observed reflections with I 2σ（I） and R = 0.0341 and wR = 0.0832 for all data. The title complex exhibits an infinite chain-like structure through bridging isonicotinate-N-oxide. Strong interchain hydrogen bonds between isonicotinate-N-oxide and H2biim result in the robust 3-D supramolecular architecture. Moreover, the complex shows strong photoluminescence with emission maximum at λ = 401 nm upon λex = 330 nm.

Synthesis, Crystal Structure, and Fluorescent and Thermal Stability Properties of Two New Cobalt(Ⅱ) Complexes with 2,2’-Bipy as Ligand

Two new cobalt(Ⅱ)complexes[Co2(2,2?-bipy)2(dpa)2(H2O)5]·4H2O(1)and Co(2,2?-bipy)3(SO4)]·7.5H2O(2)have been synthesized with diaphonic acid(H2dpa)and 2,2?-bipyridine(2,2?-bipy)as ligands.In 1,two neighboring cobalt(Ⅱ)ions are linked together by one bridging diaphonic acid group,forming an asymmetric dinuclear structure.1 crystallizes in triclinic,space group P1 with a=9.825(6),b=13.007(8),c=19.586(1)A,α=80.773(1)o,β=77.065(1)o,γ=85.902(1)o,Mr=431.4,V=2406.5(3)A^3,Dc=1.48 g/cm^3,Z=2,μ(Mo Kα)=0.767 mm-1,F(000)=1112,the final R=0.0379 and wR=0.0862.The central cobalt(Ⅱ)ions in 1 and 2 are coordinated with six atoms,forming distorted octahedral coordination geometry.The fluorescence and thermal stability properties of 1 and 2 are also reported.

Synthesis,Crystal Structure and Fluorescent and Thermal Stability Properties of the Zinc(Ⅱ) Complex [Zn(C_(15)H_(11)O_3)_2(C_(12)H_8N_2)_2]·5H_2O

A new complex has been synthesized with o-methylbenzoyl-benzoic acid（HL） and 1,10-phenanthroline（phen） in the mixture of water and ethanol. It crystallizes in monoclinic, space group C2/c with a = 13.6328（18）, b = 17.7876（18）, c = 19.998（2）, β = 104.720（4）o, C54H48N4O11Zn, Mr = 994.33, V = 4690.2（9）3, Dc = 1.408 g/cm3, Z = 4, F（000） = 2072, μ（MoKα） = 0.59 mm-1, R = 0.0736 and wR = 0.2029. The crystal structure shows that the zinc ions are coordinated with two oxygen atoms from two HL molecules and four nitrogen atoms from two phen molecules, forming distorted octahedral coordination geometry. The fluorescent and thermal stability properties of the complex are studied. The result shows that it has one fluorescent emission band at around 412 nm. In addition, the complex is stable under 210 ℃.

基于一维锌(Ⅱ)配位聚合物的水中2,4,6-三硝基苯酚和氟啶胺的选择性检测

以1,1’∶4’,1’’∶4’’,1’’’-四联苯-2,4,2’’’,4’’’-四羧酸(H_(4)L)和4,4’-联吡啶(4,4’-bpy)为配体,采用水热法合成了一维锌配位聚合物[Zn_(2)(H_(2)L)_(2)(4,4’-bpy)2(H_(2)O)]n(1),并通过单晶X射线衍射分析、元素分析、红外光谱分析和热重分析等方法对其结构进行了表征。单晶结构分析表明1属于三斜晶系,空间群为P1。配合物1含有2种配位构型不同的锌离子,分别处于扭曲的三角双锥{ZnNO_(4)}和八面体{ZnNO_(5)}几何构型中。配合物中2个H_(2)L^(2-)配体之间通过锌离子相互连接,构成了无限的一维zigzag平面结构。荧光传感实验表明配合物1的荧光能够被2,4,6-三硝基苯酚和氟啶胺猝灭,且具有较高的灵敏度和选择性,抗干扰性也非常好。

Study on Fluorescence Properties of Eu(Ⅲ) Cryptates

The mononuclear cryptate [Eu(H 3L F)(NO 3)(H 2O)](NO 3) 2 and the heterodinuclear cryptate [EuZnL F(DMF)](ClO 4) 2 were synthesized and characterized. The triplet state energy of the cryptand (H 3L F) was studied by phosphorescence spectrum. The fluorescent properties of Eu(Ⅲ) cryptates in MeOH solution show that the cryptand (H 3L F) can sensitize the Eu(Ⅲ) ion to luminescence and the introduction of the Zn(Ⅱ) ion into the mononuclear Eu(Ⅲ) cryptate resulted in blue shift of three ligand centered bands, increase of molar absorption coefficient and increase of the luminescence intensity of Eu(Ⅲ).

Synthesis,Crystal Structure and Fluorescence of a Three-dimensional Cd(II) Coordination Polymer [Cd(μ_(1,3)- SCN^-)_2(μ-dmpo)]_n (dmpo = 3,5-Dimethylpyridine N-Oxide)

A three-dimensional complex [Cd（μ1,3-SCN）2（dmpo）]n has been synthesized with μ1,3-SCN^- and dmpo as mixed bridge ligands. The crystal belongs to monoclinic, space group C2/c with a = 15.648（2）, b = 15.126（2）, c = 11.9773（15） A, β= 112.416（2）°, V= 2620.7（6） ,A, Z= 8, C9H9CdN3OS2, Mr = 351.71, Dc = 1.783 g/cm^3, F（000） = 1376 and μ = 1.967 mm^-1. The structure was refined to R = 0.0260 and wR = 0.0647 for 2186 observed reflections （I 〉 2σ（I））. In the crystal the Cd（Ⅱ） ions are coordinated by ,μ1,3-SCN^- bridge ligands to form the crossing chains on the adjacent planes, and these chains are further joined by μ-dmpo mono-dentate bridge ligands leading to a three-dimensional structure. The complex exhibits strong fluorescent emission property.

Two Metal-organic Coordination Polymers with Rigid Bis(triazole) Ligand： Assembly, Structures, and Fluorescence Properties

Two new coordination polymers containing rigid bis（triazole）, namely, [Ni（btb）_（0.5）（nph）（H_2O）]_n（1） and [Zn（btb）（SO_4）]_n（2）（btb = 4,4a-bis（1,2,4-triazolyl-1-yl）-biphenyl, H_2nph = 3-nitrophthalic acid） have been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a 3D trinodal（3,4,4）-connected sqc69 topology. Complex 2 presents a 2D uninodal 4-connected sql network, which is further packed into a 3D supramolecular framework by C-H···O hydrogen bonds. Thermal stabilities and fluorescence properties of two complexes have been discussed in detail.

一种CdⅡ-MOF作为传感Fe(Ⅲ)和Cr(Ⅵ)的多响应荧光探针

通过水热法合成了一种金属有机骨架[Cd_(3)(L)_(2)(H_(2)O)_(9)]·9H_(2)O(MOF1),其中H_(3)L=5-(((4-羧基苯基)氧基)甲基)苯-1,3-二甲酸,并通过单晶X射线衍射、粉末X射线衍射和元素分析对其进行了表征。MOF1表现为一个二维微孔结构,孔隙可利用体积为22.4%。荧光性能研究表明,MOF1可以用作检测Fe(Ⅲ)和Cr(Ⅵ)的荧光传感器。它具有高选择性和低检测限,而且不受其他离子的干扰。此外,通过金属有机骨架主体和目标分析物客体的紫外可见吸收光谱研究了主体配合物的选择性荧光猝灭机制。这种荧光猝灭的可能机制是荧光共振能量转移。

一种基于ICT协同AIE的Zn(Ⅱ)荧光探针

以2,2′:6′,2″-三联吡啶-4′-甲醛、4-氨基-N,N-二苯基苯胺为原料,合成了一种D-π-A型化合物L,并通过X-射线单晶测定了其晶体结构.该化合物能够发生分子内电荷转移(intramolecular charge transfer, ICT).三联吡啶具有较强的配位能力,作为Zn(Ⅱ)离子识别基团.当其与Zn(Ⅱ)发生配位后,吸电子能力增强,发生ICT所需能量降低,因此荧光明显增强并发生红移.通过电喷雾质谱、Job′s plot、荧光滴定等实验确定在检测体系中L与Zn(Ⅱ)配位的化学计量比为2∶1.由于生成的Zn(Ⅱ)配合物在THF/H2O介质中表现出聚集诱导发光(aggregation induced emission, AIE)性质.因此基于ICT协同AIE,化合物L可用于检测水介质中的Zn(Ⅱ)离子.