Formation of One-Dimensional Helical Columns and Excimerlike Excited States by Racemic Quinoxaline-Fused [7]Carbohelicenes in the Crystal

• Published in: Chemistry : a European journal Vol. 20; no. 32; pp. 10099 - 10109
• Main Authors: Sakai, Hayato, Shinto, Sho, Araki, Yasuyuki, Wada, Takehiko, Sakanoue, Tomo, Takenobu, Taishi, Hasobe, Taku
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 04-08-2014; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: Chemistry; Circular Dichroism; Columns (structural); Crystal structure; Crystallography, X-Ray; Crystals; Derivatives; Electrochemical Techniques; electrochemistry; Excitation spectra; Fluorescence; Helical; helical structures; Models, Molecular; Molecular orbitals; Quinoxalines - chemistry; Spectrometry, Fluorescence; Spectrum analysis; stacking interactions; supramolecular chemistry; stacking interactions; electrochemistry; fluorescence; supramolecular chemistry; helical structures
• DOI: 10.1002/chem.201402426
• EISSN: 1521-3765
• ISSN: 0947-6539

A series of quinoxaline‐fused [7]carbohelicenes (HeQu derivatives) was designed and synthesized to evaluate their structural and photophysical properties in the crystal state. The quinoxaline units were expected to enhance the light‐emitting properties and to control the packing structures in the crystal. The electrochemical and spectroscopic properties and excited‐state dynamics of these compounds were investigated in detail. The first oxidation potentials of HeQu derivatives are approximately the same as that of unsubstituted reference [7]carbohelicene (Heli), whereas their first reduction potentials are shifted to the positive by about 0.7 V. The steady‐state absorption, fluorescence, and circular dichroism spectra also became redshifted compared to those of Heli. The molecular orbitals and energy levels of the HOMO and LUMO states, calculated by DFT methods, support these trends. Moreover, the absolute fluorescence quantum yields of HeQu derivatives are about four times larger than that of Heli. The structural properties of the aggregated states were analyzed by single‐crystal analysis. Introduction of appropriate substituents (i.e., 4‐methoxyphenyl) in the HeQu unit enabled the construction of one‐dimensional helical columns of racemic HeQu derivatives in the crystal state. Helix formation is based on intracolumn π‐stacking between two neighboring [7]carbohelicenes and intercolumn CH⋅⋅⋅N interaction between a nitrogen atom of a quinoxaline unit and a hydrogen atom of a helicene unit. The time‐resolved fluorescence spectra of single crystals clearly showed an excimerlike delocalized excited state owing to the short distance between neighboring [7]carbohelicene units.
π‐Stacked helices: Quinoxaline‐fused [7]carbohelicenes (HeQu derivatives) were designed and synthesized to evaluate their structural and photophysical properties in the crystal state. A racemic HeQu derivative formed one‐dimensional helical columns in the crystal and showed an excimerlike delocalized excited state owing to the short distance between neighboring [7]carbohelicene units (see figure).