新型稀土配位聚合物{Ln_2(m-bdc)_3(H_2O)_2}_n(Ln=Ce,Nd)的合成、结构和动力学分析

Synthesis,Structure and Kinetic Analysis of New Lanthanide Complexes {Ln_2(m-bdc)_3(H_2O)_2}_n(Ln=Ce,Nd)

以Ln(NO3)3.6H2O[Ln=Ce(1),Nd(2)]、间苯二甲酸(m-H2bdc)为原料,用水-DMF溶剂热合成法合成了两个异质同构的新型三维孔洞稀土金属配位聚合物{Ln2(m-bdc)3(H2O)2}n[Ln=Ce(1),Nd(2)],晶体结构经X射线单晶衍射仪分析确定,两种配合物的晶系均为单斜晶系,P21/c空间群,配位聚合物1:a=1.35428(11)nm,b=1.45987(11)nm,c=1.67101(10)nm,β=127.750(4)°,V=2.6122(3)nm3,Z=4,Dc=2.056 g.cm-3。配位聚合物2:a=1.34364(3)nm,b=1.45406(3)nm,c=1.66669(5)nm,β=127.382(2)°,V=2.5875(11)nm3,Z=4,Dc=2.097 g.cm-3。对配位聚合物1和2进行了元素分析、热重、红外光谱等表征,同时对标题配位聚合物的热稳定性及动力学进行了分析。

Two new Lanthanide complexes { Ln2 （ m-bdc）3 （ H20）2 }n [ Ln = Ce （ 1 ）, Nd （2） ]were obtained by the solvent thermal synthesis reaction of Ln （ NO3 ） 3 ·6H20 [ Ln = Ce （ 1 ）, Nd （ 2 ） ], m- Phthalic acid （m-H2bdc） with 1：1 mole ratio. Single-crystal X-ray diffraction analysis reveals that both the crystals belong to monoclinic ,space group P21/c. For complex 1 ：a = 1. 35428（ 11 ） nm, b = 1. 45987 （11） nm, c=1.67101（10） nm,β=127.750（4）°, V=2.6122（3） nm3, Z=4, Do =2.056 g · cm-3 the final R1 = 0.0357, and wR2 = 0. 0841 for 3952 observed reflections with I 〉 2σ（ I ）. For complex 2 ： a=1.34364（3） nm, b=1.45406（3） nm, c=1.66669（5） nm,/3=127.382（2）°, V=2.5875（11） nm3, Z = 4, Do = 2. 097 g σ cm-3, the final R1 = 0. 0343, and wR2 = 0. 1259 for 4230 observed reflections with I 〉 2σ （ I ）. The structure and property of complexes have been characterized by elemental analysis, thermal analyses, IR spectra and Fluorescence. The single crystal structures show that the two complexes are isomorphic and have two-dimensional hole structures and hydrogen bondsresult in three-dimensional supramolecular structures, the coordination number of central ion Ln （ Ⅲ） is seven（ Lnl ） and eight （Ln2）. In addition, thermal stability and dynamics of two complexes were analyzed and pyrolysis kinetic parameters were got.