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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 novel complexes, Nd (oba) (H2O) 2, were synthesized by the hydrothermal method. H 2 O (1) and Sm (oba) ’- oxybiphenyl dicarboxylic acid, phen = 1, 10-phenanthroline). X-ray single crystal diffraction analysis showed that the two complexes are monoclinic, C2 / c space group. The lattice parameters of complex 1 are as follows: a = 2.73680 (5) nm, b = 0.95635 (2) nm, c = 2.17093 (4) nm, β = 97.685 0 , Z = 8, F (000) = 2 854, R (int) = 0.022 6. The 4,4’-oxydiphthalate in complex 1 has two forms: the fully deprotonated 4,4’-oxydiphthalate (oba) and the partially deprotonated 4,4’-oxydiphosphate Phthalate (Hoba). Ligands oba and Hoba bridge adjacent Nd3 + ions to form a 2D mesh with a novel {42.6} {43.6.84.102} {4} topology. Each Nd3 + ion coordinates with 8 O atoms, of which 6 O atoms come from the carboxyl groups of the ligands oba and Hoba and the other 2 O atoms come from two coordinated water. Hoba and coordination water, Hoba and Hoba form a hydrogen bond between the 2D network further into a 3D supramolecular structure. The lattice parameters of complex 2 are as follows: a = 1.35260 (5) nm, b = 1.93686 (6) nm, c = 2.72859 (8) nm, β = 99.867 = 8, F (000) = 3 368, R (int) = 0.039 4. The 4,4’-oxydiphthalate in the complex 2 also exists in two forms of oba and Hoba. The adjacent Sm3 + ions form dimeric units through carboxyl COO-bridging. The dimeric units are bridged by oba ligand to form 1D Chain structure. Each Sm3 + ion coordinates with six carboxyl O atoms from the ligands oba and Hoba and the N atom of phen. Hydrogen bonds formed between the carboxyl groups of the ligand Hoba link the 1D chain into a 2D network, and the 3D supramolecular structure is further constructed through π-π interaction between the phen molecules. The UV-vis spectra of complex 1 show that there are two absorption bands at 510-583 nm and 566-600 nm, corresponding to 4I9 / 2 → 4G7 / 2 + 4G9 / 2 + 2K13 / 2 and 4I9 / 2 → 4G5 / 2 + 4G7 / 2. The fluorescence spectra of complex 2 show the characteristic transitions of 4G5 / 2 → 6H5 / 2,4G5 / 2 → 6H7 / 2 and 4G5 / 2 → 6H9 / 2 for Sm3 + ions.