TY - DATA T1 - C‑Shaped Diastereomers Containing Cofacial Thiophene-Substituted Quinoxaline Rings: Synthesis, Photophysical Properties, and X‑ray Crystallography PY - 2014/05/16 AU - Catherine R. DeBlase AU - Ryan T. Finke AU - Jonathan A. Porras AU - Joseph M. Tanski AU - Jocelyn M. Nadeau UR - https://acs.figshare.com/articles/journal_contribution/C_Shaped_Diastereomers_Containing_Cofacial_Thiophene_Substituted_Quinoxaline_Rings_Synthesis_Photophysical_Properties_and_X_ray_Crystallography/2290981 DO - 10.1021/jo500053m.s001 L4 - https://ndownloader.figshare.com/files/3927502 KW - thiophene KW - interaction KW - UV KW - quinoxaline KW - emission KW - emissive diastereomeric compounds KW - NMR spectroscopy KW - cofacial N2 - Synthesis and characterization of two diastereomeric C-shaped molecules containing cofacial thiophene-substituted quinoxaline rings are described. A previously known bis-α-diketone was condensed with an excess of 4-bromo-1,2-diaminobenzene in the presence of zinc acetate to give a mixture of two C-shaped diastereomers with cofacial bromine-substituted quinoxaline rings. After chromatographic separation, thiophene rings were installed by a microwave-assisted Suzuki coupling reaction, resulting in highly emissive diastereomeric compounds that were studied by UV–vis, fluorescence, and NMR spectroscopy, as well as X-ray crystallography. The unique symmetry of each diastereomer was confirmed by NMR spectroscopy. NMR data indicated that the syn isomer has restricted rotation about the bond connecting the thiophene and quinoxaline rings, which was also observed in the solid state. The spectroscopic properties of the C-shaped diastereomers were compared to a model compound containing only a single thiophene-substituted quinoxaline ring. Ground state intramolecular π–π interactions in solution were detected by NMR and UV–vis spectroscopy. Red-shifted emission bands, band broadening, and large Stokes shifts were observed, which collectively suggest excited state π–π interactions that produce excimer-like emissions, as well as a remarkable positive emission solvatochromism, indicating charge-transfer character in the excited state. ER -