Citation: LIU Xiao-Jun, LIN Tao, GAO Shao-Wei, MA Rui, ZHANG Jin-Yue, CAI Xin-Chen, YANG Lei, TENG Feng. TDDFT Investigation and Design for Fluorescent Molecules with Push-Pull Structures[J]. Acta Physico-Chimica Sinica, ;2012, 28(06): 1337-1346. doi: 10.3866/PKU.WHXB201204092 shu

TDDFT Investigation and Design for Fluorescent Molecules with Push-Pull Structures

LIU Xiao-Jun ^1,2, ,
LIN Tao ¹ ,
GAO Shao-Wei ¹ ,
MA Rui ¹ ,
ZHANG Jin-Yue ¹ ,
CAI Xin-Chen ¹ ,
YANG Lei ¹ ,
TENG Feng ¹

1.
1. Key Laboratory of Luminescence and Optical Information, Ministry of Education, Institute of Optoelectronic Technology, Beijing Jiaotong University, Beijing 100044, P. R. China;
2. Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China

Received Date: 14 February 2012
Available Online: 9 April 2012
Fund Project: 国家自然科学基金(21003009) (21003009) 北京交通大学(2009JBZ019-4, 本科生创新实验项目) (2009JBZ019-4, 本科生创新实验项目)

The electronic and geometrical structures of the ground and excited states of six fluorescent emitters, namely 3-(dicyanomethylene)-5,5-dimethyl-1-(3-[9-(2-ethyl-hexyl)-carbazol]-vinyl) cyclohexene (DCDHCC), DCDHCC2, 3-(dicyanomethylene)-5,5-dimethyl-1(4-diphenylamino-styryl) cyclohexene (DCDPC), DCDPC2, 3-(dicyanomethylene)-5,5-dimethyl-1-(4-[9-carbazol]-styryl)cyclohexene (DCDCC), and 3-(dicyanomethylene)-5,5-dimethyl-1-(4-dimethylamino-styryl)cyclohexene (DCDDC) which were specifically designed for organic light-emitting diodes (OLEDs), were studied using density functional theory (DFT) and time-dependent DFT (TDDFT) in conjunction with polarizable continuum models (PCMs). Five hybrid functionals, PBE0, M06, BMK, M062X, and CAM-B3LYP, were used and compared. The experimental spectra of the molecules in acetone solvent were precisely reproduced with the BMK functional. The ionization potential and the electron affinity were calculated to access the properties of the molecules in charge injection. It was found that, when double π-bridges and acceptors were used, the emission of emitters red-shifted to the optimal emitting region. Two brand new molecules, DCDCC2 and DCDDC2, which are the double-branched counterparts of DCDCC and DCDDC, respectively, have been designed. The calculated properties of DCDCC2 and DCDDC2 in spectra and charge injection suggested that they would be as effective in their capacities as fluorescent emitters as the above six emitters.
- Density functional theory,
- Time-dependent density functional theory,
- Polarizable continuum model,
- Fluorescent molecule,
- Molecular design
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