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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (14): 1263-1268. 上一篇    下一篇

研究论文

含氯不对称配体8-羟基喹啉铝配合物电子和光谱性质的TDDFT研究

阚玉和*1 2，朱玉兰1，侯丽梅1 2，苏忠民*2   

  1. (1淮阴师范学院化学系 江苏省低维材料化学重点建设实验室 淮安 223300)
    (2东北师范大学化学学院功能材料化学研究所 长春 130024)
  • 投稿日期:2004-11-23 修回日期:2005-03-25 发布日期:2010-12-10
  • 通讯作者: 苏忠民

Electronic Structure and Optical Spectra of Tris(8-hydroxyquinolinato)aluminum Derivative with Mixed Ligand Containing Chlorine: A TDDFT Study

KAN Yu-He*1,2, ZHU Yu-Lan1, HOU Li-Mei1,2, SU Zhong-Min*2   

  1. (1 Department of Chemistry, Huaiyin Teachers College, Jiangsu Province Key Laboratory for Chemistry of Low-Dimensional Materials, Huai'an 223300)
    (2 Institute of Functional Material Chemistry, Northeast Normal University, Changchun 130024)
  • Received:2004-11-23 Revised:2005-03-25 Published:2010-12-10
  • Contact: SU Zhong-Min

PDF

1200

被引次数

34

以含时密度泛函理论(TDDFT) B3LYP方法通过电子结构计算研究了含氯不对称配体8-羟基喹啉铝配合物AlQ(ClQ)2的吸收和发射光谱性质. 计算表明, 第一激发态与基态结构变化主要集中在单一含氯配体中, 与mer-AlQ3相比, 前线占有轨道离域程度变大而未占据轨道则定域化程度提高. 最大吸收主要来自配体内电荷转移跃迁, 电荷从苯酚环和氯向含氮的吡啶环跃迁. 电子陷入态计算表明, 抽取电子能量比AlQ3相应值略大, 与实验结果一致.

关键词: 8-羟基喹啉铝衍生物, 电子光谱, 激发态, 含时密度泛函

Absorption and emission properties of novel mixed ligand complex, AlQ(ClQ)2 (Q＝8-quinolinolate, ClQ＝5,7-dichloro-8-quinolinolate) were investigated with electronic structure calculations by time-dependant density functional theory (TDDFT) B3LYP method. The optimized lowest excited state structure has an interesting feature in that only one 5,7-dichloro-8-quinolinolate ligand distorts appreciably, while the others keep their ground state structures. It is more evident that the delocalization in HOMO and localization in LUMO compared with AlQ3. The maximal absorption band could be assigned mainly to intra-ligand charge transfer transition character. It mostly originated from transitions starting from the phenoxide side containing chlorine to pyridyl side. The calculation of anion state showed that it has a higher electron extraction potential than AlQ3, which agreed with experimental result.

Key words: tris(8-hydroxyquinolinato)aluminum derivative, electronic spectrum, excited state, TDDFT