SIOC English
化学学报
高级检索

化学学报 ›› 2009, Vol. 0 ›› Issue (1): 33-38. 上一篇    下一篇

研究论文

系列IrR(CO)(PH3)2(mnt)配合物的基态和激发态结构及光谱性质的理论研究

吴玉辉王嵩白福全2,张建坡张红星2,孙家钟3   

  • 投稿日期:2008-03-14 修回日期:2008-05-15 发布日期:2009-12-30
  • 通讯作者: 张红星 E-mail:zhanghx@mail.jlu.edu.cn;zhanghx@jlu.edu.cn
  • 基金资助:
    20573042;20333050;国家级.国家自然科学基金

Theoretical Studies on the Ground- and Excited-state Structures and the Spectroscopic Properties of IrR(CO)(PH3)2(mnt) Complexes

  • Received:2008-03-14 Revised:2008-05-15 Published:2009-12-30

PDF

972

应用MP2和CIS方法分别优化了IrR(CO)(PH3)2(mnt) (mnt=maleonitriedithiolate; R=H(1), CH3(2), Br(3))系列配合物的基态和激发态几何结构。使用TD-DFT方法计算了配合物的吸收和发射光谱，结合PCM方法考虑了溶剂化效应对光谱的影响。计算结果指出：配合物1-3在430, 435及439 nm处的最低能吸收均被指认为ILCT/LLCT/MLCT的混合跃迁性质；它们的最低能磷光发射性质和吸收相似，发射能红移至760, 770和800 nm。配合物2与 1的几何结构、光谱性质都很接近，而配合物3中，由于溴的引入使其基态和激发态几何构型和前线分子轨道成份与1和2有很大不同，进而对其光谱及其跃迁性质产生了影响。

关键词: Ir配合物, 激发态, 溶剂化效应, TD-DFT

Abstract: MP2 and CIS methods were used to optimize the ground- and excited-state structures of (IrR(CO)(PH3)2(mnt) complexes, (mnt=maleonitriedithiolat e; R= H(1), Me(2), and Br(3)). The absorption and emission spectra were calculated using TD-DFT method with the PCM solvent model at the B3LYP level. The calculated results indicated that the lowest-energy absorption of 1-3 at 430, 435 and 439 nm were all assigned as the admixture of the ILCT/LLCT/MLCT transitions. The emissions are red-shifted to 760, 770 and 800 nm, the origin of which is similar to those of lowest-energy absorptions. The structure and spectroscopic properties of 2 and 1 are close to each other, but the introduction of Br in 3 changes the geometry of ground-state and excited-state and frontier orbitals, which affects the emission spectra and transition characters.

Key words: Ir complexes, excited state, solvent effect, TD-DFT