Order of magnitude effects of thiazole regioisomerism on the near-IR two-photon cross-sections of dipolar chromophores

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journal

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Author(s)

  • Karin Schmidt
  • Amalia Leclercq
  • Egbert Zojer
  • PaDreyia V. Lawson
  • Sei-Hum Jang
  • Stephen Barlow
  • Seth R. Marder
  • Jean-Luc Bredas

Detail(s)

Original languageEnglish
Pages (from-to)794-801
Journal / PublicationAdvanced Functional Materials
Volume18
Issue number5
Publication statusPublished - 11 Mar 2008
Externally publishedYes

Abstract

We have investigated computationally the two-photon absorption (2PA) properties of donor-acceptor dipolar chromophores the conjugated backbones of which contain two five-membered heterocyclic groups which may be electron-rich (thiophene-2,5-diyl) and/or electron-deficient (thiazole-2,5-diyl). Quantum-chemica, calculations (INDO/MRDCI/S-tensor and Sum-Over-State calculations based on DFT-optimized geometries) indicate that the two-photon cross-sections into the lowest two excited states S1 and S 2 can be turned by more than an order of magnitude by varying the nature, order, and, in the case of thiazole, orientation of the heterocycles. Going from one thiazole regioisomer to the other has the strongest impact on the 2PA spectra and can even invert the ratio between the 2PA cross-section of S1 and S2. An essential-state analysis reveals that different channels dominate 2PA into S1 and S2. The sensitivity of 2PA into S1 towards the orientation of the thiazole ring stems from a local modulation on the thiazole ring of the change in state dipole moment upon excitation to S1, Δμ01, whereas the dominant essential parameter through which the thiazole orientation affects 2PA into S2 is the transition dipóle moment between S1 and S2, μ12. © 2008 WILEY-VCH Verlag GmbH & Co. KGaA.

Citation Format(s)

Order of magnitude effects of thiazole regioisomerism on the near-IR two-photon cross-sections of dipolar chromophores. / Schmidt, Karin; Leclercq, Amalia; Zojer, Egbert; Lawson, PaDreyia V.; Jang, Sei-Hum; Barlow, Stephen; Jen, Alex K.-Y.; Marder, Seth R.; Bredas, Jean-Luc.

In: Advanced Functional Materials, Vol. 18, No. 5, 11.03.2008, p. 794-801.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journal