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Stereochemical Effects on Platinum Acetylide Two-Photon Chromophores.
Shelton, Abigail H; Valandro, Silvano R; Price, Randi S; Dubinina, Galyna G; Abboud, Khalil A; Wicks, Geoffrey; Rebane, Aleksander; Younus, Muhammad; Schanze, Kirk S.
Afiliação
  • Shelton AH; Department of Chemistry , University of Florida , P.O. Box 117200, Gainesville , Florida 32611 , United States.
  • Valandro SR; Department of Chemistry , University of Texas at San Antonio , San Antonio , Texas 78249 , United States.
  • Price RS; Department of Chemistry , University of Florida , P.O. Box 117200, Gainesville , Florida 32611 , United States.
  • Dubinina GG; Department of Chemistry , University of Florida , P.O. Box 117200, Gainesville , Florida 32611 , United States.
  • Abboud KA; Department of Chemistry , University of Florida , P.O. Box 117200, Gainesville , Florida 32611 , United States.
  • Wicks G; ILX Lightwave , Bozeman , Montana 59717 , United States.
  • Rebane A; Physics Department , Montana State University , Bozeman , Montana 59715 , United States.
  • Younus M; Physics Department , Montana State University , Bozeman , Montana 59715 , United States.
  • Schanze KS; National Institute for Chemical Physics and Biophysics , Tallinn , 12618 , Estonia.
J Phys Chem A ; 123(43): 9382-9393, 2019 Oct 31.
Article em En | MEDLINE | ID: mdl-31589439
ABSTRACT
A series of cis-platinum(II) acetylide complexes containing two-photon-absorbing chromophores have been synthesized and characterized to explore the effects of stereochemistry on the nonlinear absorption properties. The molecules feature 4-(phenylethynyl)phenylethynylene (PE2), diphenylaminofluorene (DPAF), and benzothiazolylfluorene (BTF) ligands. The photophysical properties were investigated under one- and two-photon conditions and compared to the known trans analogues via UV-visible absorption, photoluminescence, femtosecond and nanosecond transient absorption (TA), nanosecond z-scan, and femtosecond two-photon absorption (2PA). The bent cis complexes exhibit blue shifts in the absorption, emission, femtosecond, and nanosecond TA spectra along with lower molar extinction coefficients and lower phosphorescence yields relative to the trans complexes suggesting less efficient Pt-induced spin-orbit coupling and intersystem crossing in the cis configuration. The cis chromophores are noncentrosymmetric and therefore show dipolar behavior with a pronounced 2PA in the 0-0 transition of the S0 → S1 band, while the trans complexes show quadrupolar behavior with a forbidden 0-0 transition. In the S0 → Sn region, both cis and trans complexes show intense two-photon-absorption bands (up to 3700 GM by the peak cross section for cis-BTF) which contain a significant contribution from the excited state absorption (S1 → Sn). All six complexes exhibit comparable nonlinear absorption response with a significant contribution from triplet-triplet absorption that slightly favors trans complexes but is more strongly dependent upon the structure of the π-conjugated chromophore.

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: J Phys Chem A Ano de publicação: 2019 Tipo de documento: Article

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: J Phys Chem A Ano de publicação: 2019 Tipo de documento: Article