高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

F取代金属铂配合物电子结构和电子光谱的理论研究

刘晓冬1,2, 封继康1,2, 任爱民1, 杨兵3, 许海3   

    1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春130021;
    2. 化学学院,
    3. 超分子结构与材料国家重点实验室, 长春 130012
  • 收稿日期:2007-01-02 修回日期:1900-01-01 出版日期:2008-03-10 发布日期:2008-03-10
  • 通讯作者: 封继康

Theoretical Investigation for the Electronic Structure and Electronic Spectrum of F-substituted Pt(Ⅱ) Complexes

LIU Xiao-Dong1,2, FENG Ji-Kang1,2*, REN Ai-Min1, YANG Bing3, XU Hai3   

    1. State Key Laboratory of Theoretical and Computational Chemistry, Instutute of Theoretical Chemistry, Jilin University, Changchun 130021;
    2. College of Chemistry,
    3. State Key Laboratory of Supramolecular Structure and Material, Jilin University, Changchun 130012, China
  • Received:2007-01-02 Revised:1900-01-01 Online:2008-03-10 Published:2008-03-10
  • Contact: FENG Ji-Kang

PDF (PC)

被引次数

7

摘要： 运用Gaussian 03量子化学程序包, 采用密度泛函理论(DFT)B3LYP/LanL2DZ方法, 对重要的磷光材料金属铂配合物的结构与电子光谱进行了研究, 通过对基态结构前线分子轨道成分的分析, 指认与发光有关的低能吸收全部是金属到配体的电荷跃迁(MLCT)和配体到配体跃迁(LLCT)的混合跃迁. 在配体的苯环上引入F原子可使配合物的前线轨道能级降低, 其降低程度及对LUMO-HOMO能隙的影响与F所连的位置有关. 配体苯环的2位和4位引入F后, HOMO能级降低程度大, HOMO-LUMO能隙变大; 而F取代配体苯环3位和5位的氢使LUMO能级降低较多, 使能隙变小. 能隙的改变导致2位和4位的F取代配合物的吸收光谱和发射光谱均发生蓝移, 而于3位和5位F取代的配合物的吸收光谱和发射光谱均发生红移. 这就进一步证明通过改变取代基的种类和位置可以调控发光颜色.

关键词: F取代金属铂配合物, 分子轨道分析, 能级调控, 电子光谱

Abstract: The ground state, excited-state and electronic spectra in the Pt(Ⅱ)complexes, an important phosphorescent material, are studied with density functional theory(DFT)B3LYP/LanL2DZ. The low-energy absorptions are all assigned as the mixture of MLCT [d(Pt)→π*(ppy)] and LLCT [π(phenyl)→π*(ppy) or π(2,4-pentanedionato-O,O)→π*(ppy)]. It is found that F-substitutions in(2-phenylpyridinato-N,C2’) platinum(Ⅱ)(2,4-pentanedionato-O,O) result in the decrease of both HOMO and LUMO energies. Significantly, the HOMO-LUMO bandgap of F-substituent at the 2th or 4th position of phenyl in Pt complex is found to be increased, as a result its absorption and emission spectra are greatly blue-shifted. It provides an approach to control the emission color of Pt complexes by changing the substituents and their positions.

Key words: F-Substituted Pt(Ⅱ) complexes, Molecular orbital analysis, Energy level control, Electronic spectra

中图分类号: 

TrendMD: