From molecule to bulk material: Optical properties of hydrogen-bonded dimers [C12H12N4O2AgPF 6]2 and [C28H28N6O 3AgPF6]2 depend on the arrangement of the oxime moieties

Wen Dan Cheng, Dong Sheng Wu, Juan Shen, Shu Ping Huang, Zhi Xie, Hao Zhang, Ya Jing Gong

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

The dependence of the optical properties of [C12H 12N4O2AgPF6]2 (dimer-1) and [C28H28N6O3AgPF 6]2 (dimer-2) on the arrangement of the oxime moieties in the molecule and in bulk crystals was investigated by means of time-dependent density functional theory. Dimer-1 with simple pyridine oxime ligands and a wavy arrangement has a smaller dipole moment and larger transition energy between the two states, and thus smaller third-order polarizabilities and two-photon absorption cross sections. Dimer-2 with extended pyridine oxime ligands and a ladder arrangement has a larger dipole moment and smaller transition energy between the two states, and thus larger third-order polarizabilities and two-photon absorption cross sections. The lowest energy absorption band is redshifted for dimer-2 as compared with dimer-1, due to more pronounced π-π delocalization interactions and weaker hydrogen bonding in dimer-2. The electronic absorption spectra, frequency-dependent third-order polarizabilities, and two-photon absorption cross sections involve significant contributions from charge transfers from π/π* orbitals of the pyridine oxime ligands but no contribution from PF6- ions or H2O molecules in the wavelength range studied for the monomers and dimers of the C12H12N4O2AgPF 6 and C28H28N6O3AgPF 6 molecules. The third-order susceptibilities and two-photon absorption coefficients of bulk solids were estimated on the basis of the optical properties of the corresponding dimers, and the bulk material constructed from dimer-2 has the larger optical parameters of the two.

Original languageEnglish (US)
Pages (from-to)5151-5159
Number of pages9
JournalChemistry - A European Journal
Volume13
Issue number18
DOIs
StatePublished - 2007
Externally publishedYes

Keywords

  • Density functional calculations
  • Hydrogen bonds
  • Nonlinear optics
  • Oxime ligands
  • Silver

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