Synthesis, Photophysical Behavior, and Electronic Structure of Push−Pull Purines

Roslyn S. Butler, Pamela Cohn, Phillip Tenzel, Khalil A. Abboud and Ronald K. Castellano*
Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, Florida 32611-7200
J. Am. Chem. Soc., 2009, 131 (2), pp 623–633
DOI: 10.1021/ja806348z
Publication Date (Web): December 29, 2008
Copyright © 2008 American Chemical Society

Abstract

Abstract Image

“Push−pull” purines have been synthesized by the introduction of electron-accepting functional groups (A = CN, CO2Me, and CONHR) to the heterocyclic C(8) position to complement typical electron-donating substituents at C(2) (D1) and C(6) (D2). 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 λmax from 355−466 nm depending on substitution pattern and solvent) with excellent linear correlations between emission energy and solvent polarity (ETN), 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 Δμge 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.

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History

  • Published In Issue January 21, 2009
  • Article ASAPDecember 29, 2008
  • Received: August 18, 2008

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