Journal of Molecular Modeling

, Volume 17, Issue 6, pp 1413–1425

A comparative study of one- and two-photon absorption properties of pyrene and perylene diimide derivatives

  • Xiao-Ting Liu
  • Yang Zhao
  • Ai-Min Ren
  • Ji-Kang Feng
Original Paper

DOI: 10.1007/s00894-010-0839-9

Cite this article as:
Liu, XT., Zhao, Y., Ren, AM. et al. J Mol Model (2011) 17: 1413. doi:10.1007/s00894-010-0839-9

Abstract

Two important classes of organic molecules, perylene diimide (PDI) and pyrene derivatives have been found to possess relatively excellent photophysical and photochemical properties and especially high two-photon absorption cross sections (δTmax). Herein, one-photon absorption (OPA) and two-photon absorption (TPA) properties of some novel PDI and pyrene derivatives were comparatively investigated by the density functional theory (DFT) and Zerner’s intermediate neglect of differential overlap (ZINDO) methods. The calculated results indicate that with respect to PDI derivatives, the maximum TPA cross-sections for pyrene compounds increase obviously, the maximum peaks of OPA and TPA spectra are blue-shifted, the ΔEH-L (energy gaps between the highest occupied orbital and the lowest unoccupied orbital) increase. The different π-conjugated bridges (fluorene and pyrene) and terminal groups have slight effect on the OPA properties. Nevertheless, the molecules bearing 1,6-disubstituted pyrene as the π-conjugated bridge display the largest δTmax in both series of compounds 3 and 4. Moreover, the δTmax values of molecules with benzothiazole-substituted terminal groups are larger than those of the molecules with diphenylamine, which is attributed to benzothiazole groups stabilizing the planarity of the branch parts, extending the conjugated length and increasing the π-electron delocalized extent. Furthermore, the molecular size has marked effect on OPA and TPA properties. It is worthy to mention that cruciform 8 displays the largest δTmax among all the studied molecules in the range of 600–1100 nm. This research could provide a better understanding for the origin of the linear and nonlinear optical properties, and it would be helpful to gain more information about designing two-photon absorption materials with large δTmax.

https://static-content.springer.com/image/art%3A10.1007%2Fs00894-010-0839-9/MediaObjects/894_2010_839_Figa_HTML.gif
Graphical abstract

The largest two-photon absorption (TPA) cross-section is exhibited by the cruciform 8 in the long regions among all studied molecules in this paper. TPA properties of these molecules are comparatively studied using ZINDO/SOS method. The center and the molecular size play significant roles on optical properties.

Keywords

Density functional theoryElectronic structureOptical propertiesPerylene diimide derivativesPyreneTwo-photon absorption

Supplementary material

894_2010_839_MOESM1_ESM.doc (2.4 mb)
The online version of this article contais supplementary material, which is available to authorized users. (DOC 2479 kb)

Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • Xiao-Ting Liu
    • 1
  • Yang Zhao
    • 1
  • Ai-Min Ren
    • 1
  • Ji-Kang Feng
    • 1
  1. 1.State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical ChemistryJilin UniversityChangchunPeople’s Republic of China