光学学报, 2010, 30 (6): 1827, 网络出版: 2010-06-07  

几种2取代4,5双(α呋喃基)噁唑的结构与光谱性质

Structure and Spectrum Properties of the 2-Substituted-4, 5-di(α-furyl)oxazole
作者单位
1 天水师范学院 生命科学与化学学院,甘肃 天水 741001
2 中国科学院 兰州化学物理研究所,甘肃 兰州 730000
摘要
在密度泛函DFT-B3LYP/6-31+G水平上对2甲基4,5双(α呋喃基)噁唑(化合物A)、2苯基4,5双(α呋喃基)噁唑(化合物B)、2-α呋喃基4,5双(α呋喃基)噁唑(化合物C)和2-α呋喃乙烯基4,5双(α呋喃基)噁唑(化合物D) S0基态进行构型优化,并用单取代组态相互作用方法(CIS)优化其S1激发态结构。从理论上探讨了A,B,C和D四种化合物的前线分子轨道能量、吸收和发射光谱等性质与结构的关系,并与实验值进行了对比,发现理论计算数据能够与实验结果一致,特别是采用纯密度泛函DFT-OLYP方法计算发射光谱时,理论计算数据与实验结果相差比混合密度泛函DFT-B3LYP方法更小。计算结果表明,分子共轭体系越大,前线轨道间能隙越小,吸收光谱红移越显著。
Abstract
The ground states(S0)of the 2-methyl-4,5-di(α-furyl)oxazole (compound A),2-phenyl-4,5-di(α-furyl)oxazole (compound B),2-α-furyl-4,5-di(α-furyl)oxazole (compound C) and 2-α-furan ethenyl-4,5-di(α-furyl)oxazole (compound D) were optimized with density functional theory (DFT) at B3LYP/6-31+G level,respectively. Single-excitation configuration interaction (CIS) method was used to calculate and optimize the excited states(S1)of the four compounds. The relation among the frontier molecular orbital energy,the absorption spectra,the emission spectra and the structure of the four compounds were discussed. The results show that the theoretically calculated spectrum data well agrees with the experimental value,and especially,the calculated maximum emission spectrum wavelength is more close to the experimental data when the pure density functional theory (DFT-OLYP) method is used. In addition,the frontier molecular orbital energy gap analysis indicates that the larger the conjugation system is the more distinct the red shift of absorption spectrum is.
参考文献

[1] 黄春晖,李富有,黄岩仪. 光电功能超薄膜[M]. 北京:北京大学出版社,2001. 238

    Huang Chunhui. Li Fuyou,Huang Yanyi. Ultrathin Films for Optics and Electronics[M]. Beijing:Peking University Press,2001. 238

[2] . Xiao,H. X. Li,C. X. Tan et al.. Preparation and electrochemical properties of 3-pyridinyl-6-aryl-1,2,4-triazolo [3,4-b][1,3,4]thiadiazoles[J]. Chin. Chem. Lett., 2005, 16(3): 335-337.

[3] . 3-(3′-吡啶基)-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑衍生物基态和激发态性质[J]. 物理化学学报, 2007, 23(11): 1781-1786.

    . . Properties at the ground state and excited state of 3-(3′-pyridyl)-6-aryl-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole derivatives[J]. Acta Phys.- Chim. Sin., 2007, 23(11): 1781-1786.

[4] 李会学,胥亨霞,李志锋 等. 3-苯基-6-(4-甲苯基)-1,2,4-三唑[4,3-b]-1,2,4-三嗪晶体结构及其光电性能[J]. 光学学报,2009,29(1):236-243

    Li Huixue,Xu Hengxia,Li Zhifeng et al.. Crystal structure and photoelectric properties of 3-phenyl-6-(4-methylphenyl)-1,2,4-triazolo [4,3-b]-1,2,-triazine[J]. Acta Optica Sinica,2009,29(1):236-243

[5] . 2-取代-4,5-双(α-呋喃基)噁唑的合成及发光性能的研究[J]. 有机化学, 2008, 28(9): 1611-1615.

    . . Synthesis of 2-substituted-4,5-di(α-furyl)oxazole and their luminescent property[J]. Chin. J. Org. Chem., 2008, 28(9): 1611-1615.

[6] . W. Tang,S. A. van Slyke. Organic electroluminescent diodes[J]. Appl. Phys. Lett., 1987, 51: 913-915.

[7] . Emil,C. J. Prakash,A. Hans. Density functional study of triazole and thiadiazole systems as electron transporting materials[J]. Chem. Phys., 2006, 330: 166-171.

[8] J. Emil,C. J. Prakash,A. Hans. Chain length dependence of singlet and triplet excited states of oligofluorenes:a density functional study[J]. Chem. Phys.,2007,336(2-3):91-98

[9] B. Michel,W. Salem,L. Mario et al.. Emission energies and photophysical properties of ladder oligo(p-aniline)[J]. J. Mol. Struct.:Theochem.,2006,760(1-3):147-152

[10] 牛建钢,赵五洲,高巍 等. 立方型Ti-B-N的光学性质的计算[J]. 光学学报,2008,28(8):398-402

    Niu Jiangang,Zhao Wuzhou,Gao Wei et al.. Calculations on optical properties of cubic TiBN[J]. Acta Optica Sinica,2008,28(8):398-402

[11] 张军,韩胜元,卢贵武 等. 铌酸锂晶体电子结构和光学性质计算[J]. 中国激光,2007,34(9):1227-1231

    Zhang Jun,Han Shengyuan,Lu Guiwu et al.. Calculation for electronic structure and optical properties of LiNbO3 crystals[J]. Chinese J. Lasers,2007,34(9):1227-1231

[12] . J. Turro. Geometric and topological thinking in organic chemistry[J]. Angew. Chem. Int. Ed. Engl., 1986, 25: 882-901.

[13] . Lapouyade,W. Czeschka,W. Majenz et al.. Photophysics of donoe-acceptor substituted stilbenes. A time-resolved flourescence study using selectively bridged dimethylamino cyrano model compounds[J]. J. Phys. Chem., 1992, 96: 9643-9650.

[14] . F. Wang,S. K. Wu. Spectroscopy and photophysics of bridged enone derivatives:effect of molecular structure and solvent[J]. Photochem. Photobiol. A:Chem., 1995, 86: 109-113.

[15] M. J. Frisch,G. W. Trucks,H. B. Schlegel et al.. Gaussian 03,Revision E.01. Pittsburgh,PA:Gaussian Inc.,2004

[16] . L. A. Popelier. Characterization of a dihydrogen bond on the basis of the electron density[J]. J. Phys. Chem. A, 1998, 102(10): 1873-1878.

[17] 姜月顺,李铁津. 光化学[M]. 北京:化学工业出版社,2005. 1-7

    Jiang Yueshun,Li Tiejin. Optical Chemistry[M]. Beijing:Chemical Industry Press,2005. 1-7

[18] . Curioni,W. Andreoni. Computer simulations for organic light-emitting diodes[J]. IBM J. Res. & Dev., 2001, 45: 101-113.

[19] . 香豆素衍生物的荧光发射能计算及XC泛函的合理选择[J]. 物理化学学报, 2007, 23(12): 1831-1838.

    . Proper choice of XC functionals and calculations of fluorescence-emitting energies for coumarin derivatives[J]. Acta Phys.-Chim. Sinica, 2007, 23(12): 1831-1838.

刘艳芝, 王晓峰, 董晓宁, 李会学, 袁焜, 朱元成, 李志锋, 张俊彦. 几种2取代4,5双(α呋喃基)噁唑的结构与光谱性质[J]. 光学学报, 2010, 30(6): 1827. Liu Yanzhi, Wang Xiaofeng, Dong Xiaoning, Li Huixue, Yuan Kun, Zhu Yuancheng, Li Zhifeng, Zhang Junyan. Structure and Spectrum Properties of the 2-Substituted-4, 5-di(α-furyl)oxazole[J]. Acta Optica Sinica, 2010, 30(6): 1827.

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