【作者】 睢超霞；

【导师】 郑文杰；

【作者基本信息】 暨南大学 ， 无机化学， 2006， 硕士

【摘要】 本论文研究了噻唑类化合物2-巯基苯并噻唑（MBT）和2-氨基噻唑（AT）与过渡金属的液相配位反应，以及2-巯基苯并噻唑（MBT），2，1，3-萘并[c]硒二唑（BS），5-甲基-2，1，3-苯并[3，4-c]硒二唑（MB）和2，1，3-苯并[c]硒二唑（NS）等4种硒（硫）杂环化合物与CoCl₂，NiCl₂，CuCl₂，ZnCl₂，CdCl₂等配合物的固相合成，并对其性质进行了表征，初步探讨了其配位机理；同时对配合物的液相和固相合成进行了对比。 1．噻唑类化合物与过渡金属液相配位研究 探讨了不同极性的溶剂、不同pH值和不同金属离子对MBT和AT的紫外光谱的影响。结果表明：极性溶剂或非极性溶剂对非极性的MBT的紫外最大吸收波长的影响不大；溶剂的极性对AT有一定的影响，随着溶剂极性的增大，AT分子产生显著的增色效应。酸性环境下，pH值对MBT的紫外吸收光谱影响不大；在碱性条件下，pH值对MBT的吸收谱带有显著的影响。当在金属离子中加入MBT或是AT，n_M／n_MBT和n_M／n_AT为2∶1时紫外光谱吸收强度最小，推测是金属离子与噻唑类化合物发生了2∶1的配位作用。 2．液相和固相合成的对比 采用液相和固相方法分别合成了4种配体与CuCl₂的配合物，并用XRD、EA、ICP、IR、UV-Vis、FS等对产物进行了表征和配位机理的推测，无论采用液相或者固相反应均能合成相同的配合物，通过光谱性质表征推测配位反应发生时由于配体中的Se与Cu发生配位；另外对比液相和固相合成结果表明低热固相合成法具有操作简单、产率高、节省溶剂和节省配体等优点。 3．配合物的固相合成 在室温下，固相合成了4种硒（硫）杂环化合物与CoCl₂，NiCl₂，CuCl₂，ZnCl₂，CdCl₂形成配合物并对其进行了表征。结果表明：噻唑类配体与金属CuCl₂，CdCl₂配位比分别2∶3和3∶2，至于配位机理还需进一步探讨；硒二唑配体与CoCl₂和NiCl₂配位比均是1∶1，而与CuCl₂、ZnCl₂和CdCl₂的配位均为比2∶1；对配合物的IR吸收峰进行了归类与指认，并对配合物的紫外和荧光光谱进行讨论分析，推测硒二唑类化合物与金属发生配位的部位是v（N-Se-N）中Se原子与金属配位。 另外值得注意的是配体NS在液相和固相中均没有荧光，但是与Co和Cd配更多还原

【Abstract】 Thirteen complexes ML_XCl₂ （L= NS, MB, BS. MCl₂= CoCl₂, NiCl₂, CuCl₂, ZnCl₂, CdCl₂） were synthesized and characterization, based on the solid-phase reaction of piazselenole（NS）, 5-methyl- piazselenole（MB）, 4,5-benzopiazselenole（BS）, which acted as ligands and M as cations. Mean while, we researched spectrum characterization of 2-mercaptobenzothiazole（MBT） and 2-aminothiephene （AT） with actions.1. The coordinate MBT and AT with actions in liquid phase The influence of Uv-Vis spectrum indifferent solvents, PH and cations with 2-mercaptobenzothiazole（MBT） and 2—aminothiephene （AT） . The conclusion showed that the absorb wavelength of MBT has no change in polarity solvents or non-polarity solvents, but to AT there was a significantly hyperchromic effect. Acidity has no influence to MBT but to alkalescence, the absorption intensity reached the minimum when the proportion of n_M/n_MBT:n_M/n_AT is 2:1. We conferred that the cation and MBT produced coordinate effect.2. compare solid phase and liquid phase synthesis A series of complexes were synthesized using MBT, NS, MB, BS as ligands and Cu²⁺ as cation in liquid-phase and solid-phase reaction. The complexes were characterized and compared by ICP-AES, EA, IR, UV-Vis, XRD etc. The coordinating mechanism and the spectral properties are also discussed. The synthetical yield in solid-phase synthesis is higher than that in liquid-phase.3. Solid phase synthesis At room temperature, thirteen complexes were synthesized in solid phase, inspected and characterized with XRD, EA. The results showed that the mole ratio of three ligands to CoCl₂, NiCl₂ were 1:1 and to CuCl₂, ZnCl₂, CdCl₂ were 2:1, The IR, UV-Vis and FS of complexes were investigated. Their IR peaks were classified as the corresponding groups or bonds; The relation of their structure with the conjugative effects, absorbtion wavelength and molar absorb coefficients were discussed with the UV-Vis and FS. We conferred that it was most likely that the coordination site was M²⁺ and selenium atom. The fluorescence data indicated that更多还原