[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]·0.5bipy·3H2O配合物的合成、晶体结构及荧光性质

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在水-乙醇混合体系中,以2-羰基丙酸水杨酰腙(C_(10)H_(10)N_2O_4)、2,2-联吡啶(C_(10)H_8N_2,简写bipy)与Eu(NO_3)_3·4H_2O反应,首次培养出黄色单晶[Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]·0.5bipy·3H_2O.该晶体属三斜晶系,空间群为P-1,晶胞参数a=0.93392(16)nm,b=1.3100(2)nm,c=1.3895(2)nm,α=97.205(3)°,β=105.411(2)°,γ=106.364(2)°,V=15.35(2)nm~3,Z=2,μ=2.118mm~(-1),Dc=1.686Mg/m~3,F(000)=786,R=0.0116,wR=0.0507,GOF=0.995.晶体测试结果表明,该单晶结构为铕的9配位配合物,两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位;每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C=N中的氮与Eu~(3+)配位,形成两个共边的稳定五元环,另三个配位原子则分别来自三个水分子中的氧原子,该配合物在空间呈扭曲的单帽四方反棱柱,而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子,这些游离分子与配位分子之间存在大量分子内和分子间氢键,整个分子在空间呈三维网状结构.发光性能测试表明该配合物具有很好的荧光性质. (C_ (10) H_ (10) N_2O_4), 2,2-bipyridyl (C_ (10) H_8N_2, abbreviated bipy) and Eu (NO_3) _3 · H_2O_4] (H_2O) _3] · 0.5bipy · 3H_2O was firstly grown to form the yellow monocrystal [Eu (C_ (10) H_9N_2O_4) 1, cell parameter a = 0.93392 (16) nm, b = 1.3100 (2) nm, c = 1.3895 (2) nm, α = 97.205 (3) °, β = 105.411 ) °, V = 15.35 (2) nm~3, Z = 2, μ = 2.118mm -1, Dc = 1.686Mg / m~3, F (000) = 786, R = 0.0116, wR = 0.0507 , GOF = 0.995. The results of the crystal test show that the single crystal structure is a 9-coordination complex of europium, and the two 2-carbonyl propionic acid salicyloyl hydrazones participate in both the negative monovalent, the negative monovalent keto and the three water molecules ; The carbonyl oxygen in each 2- oxopropionate salicyyl hydrazone, the carbonyl oxygen in the amide group, and the nitrogen in C = N coordinate with Eu ~ (3+) to form two covalent, stable, five-membered rings , Respectively, and the other three coordination atoms come from oxygen atoms in three water molecules, respectively. The complexes are twisted in a single-capped square antiprism in space and in the asymmetric unit there is a free 2,2-dipyridyl Molecules and three water molecules, these swim The presence of a large number of inter-molecular hydrogen bonding between the molecules and ligand molecules, the entire space of a three-dimensional molecular network structure in the light emitting performance testing shows that the complex has good fluorescent properties.
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