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双缩二氨基硫脲Schiff碱配合物的合成表征及荧光性质研究

Synthesis, Characterizations and Fluorescence Propertyies of Dithiocarbohydrazones Complexes

【作者】 易炜

【导师】 建方方;

【作者基本信息】 青岛科技大学 , 应用化学, 2009, 硕士

【摘要】 设计合成了一系列新型的氨基硫脲Schiff碱衍生物配体及配合物,通过元素分析、红外光谱及核磁共振等手段进行了结构表征。得到了三种化合物(1Z,5Z)-1,5-二(1-(4-硝基苯基)亚乙基)硫代氨基脲(Ⅱb )、(1Z,5Z)-1,5-二(4-二甲氨基亚苄基)氨基硫脲(Ⅱd )、1,5-二(1-苯亚乙基)氨基硫脲(Ⅱf )的单晶结构;并测定了化合物(IIb),(IId),(IIm),(IIn)和(Ⅳ)及其配合物在乙醇溶液中的荧光发射光谱。研究结果表明:发现多数氨基硫脲Schiff碱衍生物及其金属配合物都具有较强的荧光,端基的取代基对荧光影响较大。用合成的新配体合成了多种配合物,通过元素分析、红外光谱及紫外光谱等手段对配合物进行了结构表征。得到了Ni(ebtd)2·2DMF(ebtd= (1Z,5Z)-1,5-bis(4-ethoxybenzylidene)thiocarbonohydrazide)、[Ni(dafo) (NO3)2]·4H2O(dafo= 4,5-diazafluoren-9-one)的单晶结构,并测定了它们的热稳定性。通过Mercury和Diamond两种软件对晶体结构进行分析,发现单晶IIb和IId由分子间氢键以及π-π堆积作用连接成二维平面结构和三维空间网络结构;Ni(ebtd)2·2DMF为二维平面结构;[Ni(dafo)(NO3)2]·4H2O的拓扑结构为66。

【Abstract】 A series of novel thiosemicarbazide schiff base derivatives ligands have been synthesized in the thesis. These compounds have been characterized by EA, IR, UV and 1H NMR. And we obtained three compounds crystal structures: (1Z,5Z)-1,5-bis(1-(4-nitrophenyl)ethylidene)thiocarbonohydrazide; (1Z,5Z)-1,5- bis(2-(dimethylamino)benzylidene)thiocarbonohydrazide and (1Z,5Z)-1,5-bis(1- phenylethylidene)thiocarbonohydrazide. The one-photon optical physical properties of compounds (4a), (4b), (4c) and (4d) in ethanol solvents were investigated carefully. The one-photon fluorescence quantum yield determined,and most of the ligands and its coordination complexes exhibited strong fluorescence.We synthesized other new complexes with the novel thiosemicarbazide schiff base derivatives, and these compounds have been characterized some of them by EA, IR ,NMR and X-ray. We obtained two complexes crystal structures which is Ni(ebtd)2·2DMF(ebtd=(1Z,5Z)-1,5-bis(4-ethoxybenzylidene)thiocarbonohydrazide) and [Ni(dafo) (NO3)2]·4H2O(dafo= 4,5-diazafluoren-9-one). We also studied the thermal stability of the two complexes.The topology structure of compounds were studied by Mercury and Diamond soft-wares. The datas show that crystal structure both of IIb and IId seem to be two-dimension or three-dimension network connected by the hydrogen bonds between different moleculars and theπ-πpacking effect. The topology structure of Ni(ebtd)2·2DMF is a two-dimension planar structure. The compound [Ni(dafo) (NO3)2]·4H2O looks like to be a parallelepiped, in which the node is 66.

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