Synthesis, photophysical behavior, and electronic structure of push - Pull purines

Roslyn S. Butler, Pamela Cohn, Phillip Tenzel, Khalil A. Abboud, Ronald K. Castellano

Research output: Contribution to journalArticlepeer-review

65 Scopus citations


"Push-pull" purines have been synthesized by the introduction of electron-accepting functional groups (A = CN, CO 2Me, and CONHR) to the heterocyclic C(8) position to complement typical electron-donating substituents at C(2) (D 1) and C(6) (D 2). The donor-acceptor purines show significantly altered, and overall improved photophysical properties relative to their acceptor-free precursors (A = H); these include red-shifted (20-50 nm) absorption maxima, highly solvatochromic emission profiles (em λ max from 355-466 nm depending on substitution pattern and solvent) with excellent linear correlations between emission energy and solvent polarity (E T N), improved photochemical stability upon continuous irradiation, and enhanced (up to 2500%) fluorescence quantum yields. Comprehensive structure-property studies show how the absorption/emission maxima and quantum yields depend on donor and acceptor structure, relative donor position (C(2) or C(6)), and solvent (1,4-dioxane, dichloromethane, acetonitrile, methanol, and in some cases water). Further insight regarding electronic structure comes from a quantitative treatment of the solvent-dependent emission data (that provides Δ μge values ranging from 1.9 to 3.4 D) and DFT (B3LYP/6-311++G**) electronic structure calculations. X-ray crystal structures of several derivatives showcase the molecular recognition capabilities of the donor-acceptor chromophores that overall have photophysical and structural properties suitable for applications in biosensing and materials.

Original languageEnglish (US)
Pages (from-to)623-633
Number of pages11
JournalJournal of the American Chemical Society
Issue number2
StatePublished - Jan 21 2009
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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