萘磺酸型离子配合物的合成及其分子识别性能
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摘要
常温反应条件下制备了4个基于乙二胺和1,5-萘二磺酸的配位化合物[M(en)(H_2O)_4]·1,5-nds·(H_2O)_2(M=Ni(1),Co(2),Cd(3),Cu(4),nds=1,5-萘二磺酸;en=乙二胺),并通过红外光谱、元素分析、X射线单晶衍射、X射线粉末衍射和热重分析等技术手段确定了其晶体结构。结构分析表明,该系列配合物属于同构体系,单斜晶系,C2/c空间群。以配合物1为例,其晶胞参数为a=1.69026(19)nm,b=1.01373(11)nm,c=1.3448(3)nm,α=90°,β=120.2650°,γ=90°,V=1.9901(5)nm~3,Z=4,Dc=1.713 g/cm~3,F(000)=1072,R_1=0.0326,wR_2=0.0867。该系列配合物的中心金属为六配位模式,与来自乙二胺的2个N原子和4个H_2O中的氧原子配位。游离水与磺酸氧和配位水之间存在着丰富的氢键作用,构筑成三维的网络结构。测定了以Cd为中心金属配合物3的荧光光谱,发现其在对于甲醇的小分子识别性能方面具有应用前景。
Four compounds [M( en)( H_2O)_4]·1,5-nds·( H_2O)_2( M = Ni( 1),Co( 2),Cd( 3),Cu( 4),based on ethylene diamine( en) and 1,5-naphthalenedisulfonic acid( nds),were synthesized by hydrothermal synthesis method under room temperature. The structures of the crystals were confirmed by X-ray diffraction( XRD) method and SHELXTL-97 software. The four compounds have the same three dimensional( 3D)framework in monoclinic C2/c space group,only different in metal atoms. The cell parameters of compound 1are: a = 1. 69026( 19) nm,b = 1. 01373( 11) nm,c = 1. 3448( 3) nm,α = 90°,β = 120. 2650°,γ = 90°,V = 1. 9901( 5) nm~3,Z = 4,D_c= 1. 713 g/cm~3,F( 000) = 1072,R_1= 0. 0326,wR_2= 0. 0867. One metal atom is coordinated to four oxygen atoms from water molecules and two nitrogen atoms of one ethylene diamine.There exit abundant hydrogen bonds interactions between free water molecules and oxygen atoms in 1,5-naphthalenedisulfonic acid anion. One dimensional chains were formed through abundant hydrogen bonds and one [Ni( en)( H_2O)_4]~(2 +)located between each two nds2-. The two adjacent [Ni( en)( H_2O)_4]~(2 +)arranged by the opposite mode( head to head). The properties of the two compounds were characterized by XRD,thermal gravimetric analysis( TGA), fluorescence spectroscopy and multi-function spectrometer. The molecular recognition properties of compound 3 with M = Cd in methanol solution was studied. The compound3 was solved in different solvents in which the highest strength of fluorescence spectroscopy occurs in methanol solution. The strength of fluorescence spectroscopy decreases,with increasing concentration of methanol which may have potential applications in fluorescence probe to recognize polarity.
Four compounds [M( en)( H_2O)_4]·1,5-nds·( H_2O)_2( M = Ni( 1),Co( 2),Cd( 3),Cu( 4),based on ethylene diamine( en) and 1,5-naphthalenedisulfonic acid( nds),were synthesized by hydrothermal synthesis method under room temperature. The structures of the crystals were confirmed by X-ray diffraction( XRD) method and SHELXTL-97 software. The four compounds have the same three dimensional( 3D)framework in monoclinic C2/c space group,only different in metal atoms. The cell parameters of compound 1are: a = 1. 69026( 19) nm,b = 1. 01373( 11) nm,c = 1. 3448( 3) nm,α = 90°,β = 120. 2650°,γ = 90°,V = 1. 9901( 5) nm~3,Z = 4,D_c= 1. 713 g/cm~3,F( 000) = 1072,R_1= 0. 0326,wR_2= 0. 0867. One metal atom is coordinated to four oxygen atoms from water molecules and two nitrogen atoms of one ethylene diamine.There exit abundant hydrogen bonds interactions between free water molecules and oxygen atoms in 1,5-naphthalenedisulfonic acid anion. One dimensional chains were formed through abundant hydrogen bonds and one [Ni( en)( H_2O)_4]~(2 +)located between each two nds2-. The two adjacent [Ni( en)( H_2O)_4]~(2 +)arranged by the opposite mode( head to head). The properties of the two compounds were characterized by XRD,thermal gravimetric analysis( TGA), fluorescence spectroscopy and multi-function spectrometer. The molecular recognition properties of compound 3 with M = Cd in methanol solution was studied. The compound3 was solved in different solvents in which the highest strength of fluorescence spectroscopy occurs in methanol solution. The strength of fluorescence spectroscopy decreases,with increasing concentration of methanol which may have potential applications in fluorescence probe to recognize polarity.
引文
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[3]Jiang H,Liu Y,Ma J,et al.Infinite Chains Constructed from Flexible Bis(benzimidazole)Based Ligands[J].Polyhedron,2008,27(12):2595-2602.
[4]Zhang Z,Xiang S,Rao S,et al.A Rod Packing Microporous Metal Organic Framework with Open Metal Site for Selective Guest Sorption and Sensing of Nitrobenzene[J].Chem Commun,2010,46(38):7205-7207.
[5]Dong M,Zhao M,Ou S,et al.A Luminescent Dye@MOF Platform:Emission Fingerprint Relationships of Volatile Organic Molecules[J].Angew Chem Int Ed,2014,53(6):1575-1579.
[6]Cao K,Xia Y,Wang G,et al.A Robust Luminescent Ba(Ⅱ)Metal Organic Framework Based on Ppyridine Carboxylate Ligand for Sensing of Small Molecules[J].Inorg Chem Commun,2015,53:42-45.
[7]SONG Pengyue,ZHU Jiang,YU Bohao,et al.Study on the Performance of Phosphotungstic Acid-urea/Fe3O4Magnetic Oxidative Desulfurization Catalyst[J].Chinese J Appl Chem,2015,32(3):317-321(in Chinese).宋鹏月,朱江,于博浩,等.磷钨酸-尿素/四氧化三铁磁性氧化脱硫催化剂反应性能[J].应用化学,2015,32(3):317-321.
[8]JIANG Chunjie,SUN Shengnan,WANG Xuyang,et al.Synthesis of Dimethyl Ether from Methanol over Heteropoly Acid/Nanocrystalline HZSM-5 Complex Solid Acidic Catalyst[J].Acta Chim Sin,2013,71(5):810-814(in Chinese).姜春杰,孙胜男,王旭阳,等.甲醇脱水制二甲醚的杂多酸/纳米HZSM-5复合固体酸催化剂[J].化学学报,2013,71(5):810-814.
[9]WANG Xuyang,SONG Pengyue,WANG Xiangsheng,et al.In-situ Characterization and Reactivity of Heteropoly Acidbased Catalysts for Deep Hydrodesulfurization of Fluid Catalytic Cracking Gasoline[J].Chinese J Appl Chem,2014,31(8):990-992(in Chinese).王旭阳,宋鹏月,王祥生,等.多酸基深度加氢脱硫催化剂的原位表征和反应性能[J].应用化学,2014,31(8):990-992.
[10]CHEN Lidong,LIU DI,NIU Siqi,et al.Oxidative Desulfurization of Organic Sulfides over Phosphotungstic Acid/NanoZSM-5 Composite Catalyst[J].Chinese J Appl Chem,2016,33(3):364-366(in Chinese).陈立东,刘迪,牛思祺,等.磷钨酸纳米ZSM-5复合催化剂的氧化脱硫反应性能[J].应用化学,2016,33(3):364-366.
[11]Thuery P,Harrowfield J.Uranyl Ion Complexes with Long-Chain Aliphaticα,ω-Dicarboxylates and 3d-Block Metal Counterions[J].Inorg Chem,2016,55(5):2133-2145.
[12]Eberle B,Damjanovic M,Enders M,et al.Radical Monocationic Guanidino Functionalized Aromatic Compounds(GFAs)as Bridging Ligands in Dinuclear Metal Acetate Complexes:Synthesis,Electronic Structure,and Magnetic Coupling[J].Inorg Chem,2016,55(4):1683-1696.