2,1,3-苯并噻二唑衍生物光电性质的理论研究
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摘要
研究了考虑溶剂效应后2,1,3-苯并噻二唑衍生物中S原子被CH_2—、O—和NH—取代引起的电子性质和光谱性质的变化,结果表明,与母体分子相比,O—取代引起的最高占据轨道能量(E_(HOMO))和最低空轨道能量(E_(LUMO))的变化很小,而CH_2—和NH—取代引起的E_(HOMO)和E_(LUMO)的变化较明显,且CH_2—和NH—取代后分子E_(HOMO)的变化小于E_(LUMO)的变化.CH_2—取代导致最大吸收波长(λ_(abs))和最大发射波长(λ_(em))明显红移,而O—和NH—取代导致λ_(abs)和λ_(em)明显蓝移;而且取代后分子的吸收和发射光谱的振子强度都增大.
The variation in the electronic and optical properties upon the CH_2—,O— and NH— substitutions based on the 2,1,3-benzothiadiazole derivative considering solvent effect was studied by quantum-chemical calculations. The results show that, in comparison with those of the pristine molecule, the variation on the energy of the highest occupied molecular orbital(E_(HOMO)) and the energy of the lowest unoccupied orbital(E_(LUMO)) upon O— substitution is slight, while that on the E_(HOMO) and E_(LUMO) upon CH_2— and NH— substitutions is notable. Compared with the pristine molecule, the absorption and emission spectra of CH_2— substitution exhibit red shifts, whereas those of O— and NH— substitutions exhibit blue shifts. The oscillator strengths of the absorption and emission spectra increase with respect to the pristine molecule.
The variation in the electronic and optical properties upon the CH_2—,O— and NH— substitutions based on the 2,1,3-benzothiadiazole derivative considering solvent effect was studied by quantum-chemical calculations. The results show that, in comparison with those of the pristine molecule, the variation on the energy of the highest occupied molecular orbital(E_(HOMO)) and the energy of the lowest unoccupied orbital(E_(LUMO)) upon O— substitution is slight, while that on the E_(HOMO) and E_(LUMO) upon CH_2— and NH— substitutions is notable. Compared with the pristine molecule, the absorption and emission spectra of CH_2— substitution exhibit red shifts, whereas those of O— and NH— substitutions exhibit blue shifts. The oscillator strengths of the absorption and emission spectra increase with respect to the pristine molecule.
引文
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[3] TAO P, LI W L, ZHANG J, et al. [J]. Adv Funct Mater, 2016, 26: 881-894.
[4] WU S F, LI S H, WANG Y K, et al. [J]. Adv Funct Mater, 2017, 27: 1701314.
[5] HU B, ZHANG J P. [J]. Polymer, 2009, 50: 6172-6185.
[6] HU B, ZHANG J P, Chen Y. [J]. Eur Polym J, 2011, 47: 208-224.
[7] 胡波, 刘腊梅, 张浩. [J]. 分子科学学报, 2012, 28: 79-83.
[8] HU B, YAO C, WANG Q W, et al. [J]. Sci China Chem, 2012, 55: 1364-1369.
[9] THOMAS K R J, LIN J T, VELUSAMY M, et al. [J]. Adv Funct Mater, 2004, 14: 83-90.
[10] KATO S I, MATSUMOTO T, SHIGEIWA M, et al. [J]. Chem Eur J, 2006, 12: 2303-2317.
[11] ROOTHAAN C C J. [J]. Rev Mod Phys, 1951, 23: 69-89.
[12] POPLE J A, NESBET R K. [J]. J Chem Phys, 1954, 22: 571-578.
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[14] MIERTU? S, SCROCCO E, TOMASI J. [J]. Chem Phys, 1981, 55: 117-129.
[15] MIERTU? S, TOMASI J. [J]. Chem Phys, 1982, 65: 239-245.
[16] COSSI M, BARONE V, CAMMI R, et al. [J]. Chem Phys Lett, 1996, 255: 327-335.
[17] PARR R G, YANG W. Density Functional Theory of Atoms and Molecules [M]. Oxford: Oxford University Press, 1989: 47-69.
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[19] ADAMO C, BARONE V. [J]. J Chem Phys, 1999, 110: 6158-6170.
[20] STRATMANN R E, SCUSERIA G E, FRISCH M J. [J]. J Chem Phys, 1998, 109: 8218-8224.
[21] BAUERNSCHMITT R, AHLRICHS R. [J]. Chem Phys Lett, 1996, 256: 454-464.
[22] CASIDA M E, JAMORSKI C, CASIDA K C, et al. [J]. J Chem Phys, 1998, 108: 4439-4449.
[23] HARIHARAN P C, POPLE J A. [J]. Mol Phys, 1974, 27: 209-214.
[24] GORDON M S. [J]. Chem Phys Lett, 1980, 76: 163-168.
[25] FRISCH M J, POPLE J A, BINKLEY J S. [J]. J Chem Phys, 1984, 80: 3265-3269.
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[27] FRISCH M J, TRUCKS G W, SCHLEGEL H B, et al. Gaussian 09[CP]. Gaussian Inc, Wallingford, C T, 2009.