基于4,4＇-氧联苯二甲酸配体具有{4^2·6}{4^3·6·8^4·10^2}{4}拓扑结构的2D钕和1D钐配合物的合成、晶体结构及光谱表征

Synthesis,Crystal Structures and Spectroscopic Properties of a 2D Neodymium Complex with Topology of{4^2·6} {4^3·6·8^4·10^2} {4} and a 1D Samarium Complex

通过水热法合成了2种新的配合物[Nd(oba)(Hoba)(H2O)2].H2O(1)和Sm(oba)(Hoba)(phen)(2)(H2oba=4,4'-氧联苯二甲酸,phen=1,10-邻菲啰啉)。X射线单晶衍射分析表明,2种配合物均属单斜晶系,C2/c空间群。配合物1的晶胞参数为:a=2.73680(5)nm,b=0.95635(2)nm,c=2.17093(4)nm,β=97.685 0(10)°,V=5.630 12(19)nm3,Z=8,F(000)=2 854,R(int)=0.022 6。配合物1中4,4'-氧联苯二甲酸根存在2种形式:完全脱质子的4,4'-氧联苯二甲酸根(oba)和部分脱质子的4,4'-氧联苯二甲酸根(Hoba)。配体oba和Hoba桥联相邻Nd3+离子形成具有新颖{42.6}{43.6.84.102}{4}拓扑结构的2D网。每个Nd3+离子与8个O原子配位,其中6个O原子来自配体oba和Hoba的羧基,另外2个O原子来自2个配位水。Hoba和配位水、Hoba和Hoba间形成了氢键,将2D网络进一步构筑成了3D超分子结构。配合物2的晶胞参数为:a=1.35260(5)nm,b=1.93686(6)nm,c=2.72859(8)nm,β=99.867(2)°,V=7.0426(4)nm3,Z=8,F(000)=3 368,R(int)=0.039 4。配合物2中4,4'-氧联苯二甲酸根同样存在oba和Hoba 2种形式,相邻Sm3+离子通过羧基COO-桥联形成二聚单元,二聚单元通过oba配体桥联形成1D链结构。每个Sm3+离子与6个来自配体oba和Hoba的羧基O原子以及phen的N原子配位。配体Hoba的羧基间形成的氢键将1D链连接成2D网,通过phen分子间π-π作用进一步构筑成3D超分子结构。配合物1的紫外-可见光谱表明,在510～538 nm和566～600 nm处有2个吸收带,分别对应中心Nd3+的4I9/2→4G7/2+4G9/2+2K13/2和4I9/2→4G5/2+4G7/2特征跃迁;配合物2的荧光光谱表现出Sm3+离子的4G5/2→6H5/2、4G5/2→6H7/2和4G5/2→6H9/2特征跃迁。

Two new complexes [Nd（oba）（Hoba）（H2O）2]·H2O（1） and Sm（oba）（Hoba）（phen）（2）（H2oba=4,4′-oxybis（benzoic acid）,phen=1,10-phenanthroline） were prepared by hydrothermal method.The X-ray diffraction analysis indicated that the two complexes crystallized in monoclinic system with space group C2/c.The cell parameter of complex 1 are：a=2.736 80（5） nm,b=0.956 35（2） nm,c=2.170 93（4） nm,β=97.685 0（10） °,V=5.631 02（19） nm3,Z=8,F（000）=2 854,R（int）=0.022 6.In complex 1,oba and Hoba ligands connect the neighboring Nd3＋ ions to form a 2D network with novel topology of {42·6}{43·6·84·102}{4}.Each Nd3＋ ion is eight-coordinated by six oxygen atoms from oba and Hoba ligands and two O atoms from waters.3D structure is achieved through OHO hydrogen bondings between the coordinated water molecules and Hoba and between Hoba ligands.The cell parameters of complex 2 are：a=1.352 60（5） nm,b=1.936 86（6） nm,c=2.728 59（8） nm,β=99.867（2）°,V=7.042 6（4） nm3,Z=8,F（000）=3 368,R（int）=0.039 4.In complex 2,the coordination modes of oba and Hoba are similar to those in complex 1.Sm3＋ ion is eight-coordinated by six O atoms from oba and Hoba ligands and two N atoms from phen.The two neighboring Sm3＋ ions are connected by COO-groups and form dimeric units,which are further joined by oba lignds to assemble into a 1D chain-like complex.The 2D network of complex 2 is formed through the hydrogen bondings between the uncoordinated carboxyl of the Hoba ligands.Moreover,3D superamolecular structure of complex 2 is formed through the π-π stacking interactions between phen molecules.The UV Vis spectrum of complex 1 shows characteristic transitions of Nd3＋ with4I9/2→4G7/2 ＋4G9/2＋2K13/2 and 4I9/2→4G5/2＋4G7/2 at 510~538 nm and 566~600 nm,respectively;the fluorescence spectrum of complex 2 shows characteristic emission of Sm3＋ with the transitions of 4G5/2→6H5/2,4G5/2→6H7/2 and 4G5/2→6H9/2.