以苯基吡唑为主配体的Ir配合物电子结构和光谱性质的密度泛函理论研究

高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (7): 1392.

以苯基吡唑为主配体的Ir配合物电子结构和光谱性质的密度泛函理论研究

谷新¹, 张厚玉¹, 费腾¹, 段桂花¹, 马於光¹, 刘晓冬²

1. 吉林大学超分子结构与材料国家重点实验室,
2. 吉林大学化学学院, 长春 130012

收稿日期:2008-07-03 出版日期:2009-07-10 发布日期:2009-07-10
通讯作者: 张厚玉, 男, 博士, 副教授, 主要从事理论化学研究. E-mail: houyuzhang@jlu.edu.cn; 马於光, 男, 博士, 教授, 博士生导师, 主要从事有机光电材料研究. E-mail: ygma@jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 20603013)和国家“九七三”计划(批准号: 2009CB623605)资助.

Electronic Structures and Spectroscopic Properties Studies of Phosphorescent Iridium(Ⅲ) Complexes with Phenylpyrazole Ligands by Density Functional Theory

GU Xin¹, ZHANG Hou-Yu^1*, FEI Teng¹, DUAN Gui-Hua¹, MA Yu-Guang^1*, LIU Xiao-Dong²

1. State Key Laboratory of Supramolecular Structure and Materials,
2. College of Chemistry, Jilin University, Changchun 130012, China

Received:2008-07-03 Online:2009-07-10 Published:2009-07-10
Contact: ZHANG Hou-Yu. E-mail: houyuzhang@jlu.edu.cn; MA Yu-Guang. E-mail: ygma@jlu.edu.cn
Supported by:
国家自然科学基金(批准号: 20603013)和国家“九七三”计划(批准号: 2009CB623605)资助.

摘要/Abstract

摘要：

用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)的B3LYP方法对以苯基吡唑ppz为主配体的4种Ir配合物Ir(ppz)₃, Ir(ppz)₂(acac), Ir(ppz)₂(pic)和Ir(ppz)₂(dbm)的电子结构和光谱性质进行了理论研究. 计算结果表明, 辅助配体的改变对Ir配合物的最高占据轨道(HOMO)的影响不大, 但会显著的降低分子最低空轨道(LUMO)的能级, 从而调节Ir配合物的HOMO和LUMO间的能隙. 4种配合物对应的发射跃迁分别为Ir(ppz)₃:d(Ir)+π(ppz)→π*(ppz); Ir(ppz)₂(pic):d(Ir)+(ppz)→π*(pic); Ir(ppz)₂(acac), Ir(ppz)₂(dbm):d(Ir)+π(acacdbm)→π*(acacdbm). 金属配合物的发光颜色可以通过选择合适的辅助配体调节.

关键词: Ir配合物; 辅助配体; 密度泛函理论; 分子轨道; 电子光谱

Abstract:

The electronic structures and spectroscopic properties ofphosphorescent Ir(Ⅲ) complexes Ir(ppz)₃, Ir(ppz)₂(pic), Ir(ppz)₂(acac) and Ir(ppz)₂(dbm)(ppz=phenylpyrazole, pic=picolinate, acac=Pentane-2,4-dione and dbm=dibenzoylmethane), were investigated theoretically. Density functional theory(DFT) and time dependent DFT calculations were performed on the ground and excited states of the investigated complexes to provide insight into the structural, electronic, and optical properties of these systems. Calculated results testify that ancillary ligands have little influence on the highest occupied molecular orbital(HOMO) and great effect on the lowest unoccupied molecular orbital(LUMO) by lowering the LUMO energy levels dramatically. The transition of Ir(ppz)₃ is attributed to d(Ir)+π(ppz)→π*(ppz); whereas that of Ir(ppz)₂(pic) is related to d(Ir)+π(ppz)→π*(pic); Ir(ppz)₂(acac) and Ir(ppz)₂(dbm) are categorized as d(Ir)+π(acac/dbm)→π*(acac/dbm) charge transfer. Emission color of iridium complexes could be tuned by choosing congruent ancillary ligands.

Key words: Ir complex; Ancillary ligand; Density functional theory; Molecular orbital; Electronic spectrum

TrendMD:

谷新, 张厚玉, 费腾, 段桂花, 马於光, 刘晓冬. 以苯基吡唑为主配体的Ir配合物电子结构和光谱性质的密度泛函理论研究. 高等学校化学学报, 2009, 30(7): 1392.

GU Xin, ZHANG Hou-Yu*, FEI Teng, DUAN Gui-Hua, MA Yu-Guang*, LIU Xiao-Dong. Electronic Structures and Spectroscopic Properties Studies of Phosphorescent Iridium(Ⅲ) Complexes with Phenylpyrazole Ligands by Density Functional Theory. Chem. J. Chinese Universities, 2009, 30(7): 1392.

参考文献

[1]Adachi C., Baldo M. A., Forrest S. R., et al.. Appl. Phys. Lett.[J], 2001, 78: 1622—1624
[2]Lamansky S., Djurovich P., Murphy D., et al.. J. Am. Chem. Soc.[J], 2001, 123: 4304—4312
[3]Kwong R. C., Nugent M. R., Michalski L., et al.. Appl. Phys. Lett.[J], 2002, 81: 162—164
[4]Chen F. C., Yang Y.. Appl. Phys. Lett.[J], 2002, 80: 2308—2310
[5]Tokito S., Iijima T., Tsuzuki T., et al.. Appl. Phys. Lett.[J], 2003, 83: 2459—2461
[6]Nazeeruddin M. K., Humphry B. R., Berner D., et al.. J. Am. Chem. Soc.[J], 2003, 125: 8790—8797
[7]Rayabarapu D. K., Paulose B. M. J. S., Duan J. P., et al.. Adv. Mater.[J], 2005, 17: 349—353
[8]Li H. C., Chou P. T., Hu Y. H., et al.. Organometallics[J], 2005, 24: 1329—1335
[9]Li C. L., Su Y. J., Tao Y. T., et al.. Adv. Funct. Mater.[J], 2005, 15: 387—395
[10]Okada S., Okinaka K., Iwawaki H., et al.. Dalton Trans.[J], 2005: 1583—1590
[11]Wong W. Y., Zhou G. J., Yu X. M., et al.. Adv. Funct. Mater.[J], 2006, 16: 838—846
[12]Beeby A., Bettington S., Samuel I. D. W., et al.. J. Mater. Chem.[J], 2003, 13: 80—83
[13]Jung S., Kang Y., Kim H. S., et al.. Eur. J. Inorg. Chem.[J], 2004, 43: 3415—3423
[14]Liang B., Jiang C., Chen Z., et al.. J. Mater. Chem.[J], 2006, 16: 1281—1286
[15]Lee C., Das R. R., Kim J.. Chem. Mater.[J], 2004, 16: 4642—4646
[16]Li J., Djurovich P. I., Alleyne B. D., et al.. Inorg. Chem.[J], 2005, 44: 1713—1727
[17]Takizawa S. Y., Nishida J. I., Tsuzuki T., et al.. Inorg. Chem.[J], 2007, 46: 4308—4319
[18]You Y., Park S. Y.. J. Am. Chem. Soc.[J], 2005, 127: 12438—12439
[19]LIU Xiao-Dong(刘晓冬), FENG Ji-Kang(封继康), REN Ai-Min(任爱民), et al.. Chem. J. Chinese Universities(高等学校化学学报)[J], 2006, 27(11): 2156—2159
[20]Zhao Q., Liu S., Shi M., et al.. Inorg. Chem.[J], 2006, 45: 6152—6160
[21]Hay P. J.. J. Phys. Chem. A[J], 2002, 106: 1634—1641
[22]Yang C. H., Li S. W., Chi Y., et al.. Inorg. Chem.[J], 2005, 44: 7770—7780
[23]LIU Xiao-Dong(刘晓冬), FENG Ji-Kang(封继康), REN Ai-Min(任爱民), et al.. Chem. J. Chinese Universities(高等学校化学学报)[J], 2008, 29(3): 600—604
[24]LI Xiao-Na(李晓娜), FENG Ji-Kang(封继康), REN Ai-Min(任爱民). Chem. J. Chinese Universities(高等学校化学学报)[J], 2008, 29(2): 380—384
[25]Tamayo A. B., Alleyne B. D., Djurovich P. I., et al.. J. Am. Chem. Soc.[J], 2005, 125: 7377—7387
[26]Park N. G., Choi G. C., Lee Y. H., et al.. Curr. Appl. Phys.[J], 2006, 6: 620—626
[27]Frisch M. J., Trucks G. W., Schlegel H. B., et al.. Gaussian 03, Revision B.05[CP], Wallingford CT: Gaussian, Inc., 2004
[28]Fei T., Gu X., Zhang H. Y., et al.. Synth. Met.[J], 2009, 159: 113—118