萘磺酸型离子配合物的合成及其分子识别性能

Synthesis of Ionic Coordination Compounds with Naphthalenedisulfonic Acid and Their Molecular Recognition Properties

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）（ H2O）4]·1,5-nds·（ H2O）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,Dc= 1. 713 g/cm^3,F（ 000） = 1072,R1= 0. 0326,wR2= 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）（ H2O）4]^2 ＋located between each two nds^2-. The two adjacent [Ni（ en）（ H2O）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.