A theoretical study of the ring size effect on one- and two-photon absorption properties of macrocyclic thiophene derivatives

作者：Huang, Shuang; Zou, Lu-Yi; Ren, Ai-Min^*; Guo, Jing-Fu; Liu, Xiao-Ting; Feng, Ji-Kang

来源：New Journal of Chemistry, 2012, 36(4): 947-953.

DOI：10.1039/c2nj20886e

• DENSITY-FUNCTIONAL THEORY
• BOND-LENGTH ALTERNATION
• OPTICAL-DATA STORAGE
• CONJUGATED MOLECULES
• ORGANIC-MOLECULES
• CROSS-SECTION
• PHOTON
• ENHANCEMENT
• ACETYLENE

The equilibrium geometries, electronic structures, one-and two-photon absorption (OPA and TPA) properties of macrocyclic thiophene derivatives [C[6T_A_E](n)-Me (n = 1-3)] with different ring sizes have been investigated by quantum chemistry calculation. The results indicate that as the unit number increases, the p-conjugated effect enhances, OPA maximum wavelength (lambda((1))(max)) shows a significant red-shift with increasing oscillator strength (f(0k)), and the TPA cross-section value (delta(max)) also increases, the delta(max) value of C[6T_A_E](3)-Me is twentyfold larger than that of the repeat unit C[6T_A_E]-Me. We have analyzed the internal factors influencing delta(max) such as transition dipole moments (M-0k and M-kn), the product of oscillator strengths (f(0k) x f(kn)), and the number of pi electrons (Ne) in detail. In addition, it is demonstrated that intramolecular charge transfer (ICT) is one of the intrinsic factors, but not a dominant one for the increase in TPA cross-section with regard to this system.

• 出版日期2012
• 单位东北师范大学; 吉林大学