Synthesis, photophysical behavior, and electronic structure of push-pull purines
Butler, RS; Cohn, P; Tenzel, P; Abboud, KA; Castellano, RK
| HERO ID | 1048290 |
|---|---|
| In Press | No |
| Year | 2009 |
| Title | Synthesis, photophysical behavior, and electronic structure of push-pull purines |
| Authors | Butler, RS; Cohn, P; Tenzel, P; Abboud, KA; Castellano, RK |
| Journal | Journal of the American Chemical Society |
| Volume | 131 |
| Issue | 2 |
| Page Numbers | 623-633 |
| Abstract | "Push-pull" purines have been synthesized by the introduction of electron-accepting functional groups (A = CN, CO(2)Me, 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 lambda(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 Delta mu(ge) 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. |
| Doi | 10.1021/ja806348z |
| Pmid | 19113848 |
| Wosid | WOS:000262521800052 |
| Is Certified Translation | No |
| Dupe Override | No |
| Comments | Journal: ISSN: |
| Is Public | Yes |
| Language Text | English |
| Is Qa | No |