Comparison Study of the Site-Effect on Regioisomeric Pyridyl–Pyrene Conjugates: Synthesis, Structures, and Photophysical Properties

• Published in: Journal of organic chemistry Vol. 85; no. 6; pp. 4256 - 4266
• Main Authors: Lu, Qing, Kole, Goutam Kumar, Friedrich, Alexandra, Müller-Buschbaum, Klaus, Liu, Zhiqiang, Yu, Xiaoqiang, Marder, Todd B
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 20.03.2020; Amer Chemical Soc
• Subjects: chemical reactions; Chemistry; Chemistry, Organic; isomers; moieties; organic compounds; Physical Sciences; Science & Technology; spectral analysis; X-ray diffraction; POSITION; CATALYZED BORYLATION; FLUORESCENCE; DERIVATIVES; POLYCYCLIC AROMATIC-HYDROCARBONS; ARYLATION
• ISSN: 0022-3263; 1520-6904; 1520-6904
• DOI: 10.1021/acs.joc.9b03421

To investigate the “site effect” of pyridyl substituents on a pyrene core, four regioisomeric monopyridyl-pyrene (1–4) and five regioisomeric dipyridyl-pyrene (5–9) conjugates were synthesized and characterized and their structures confirmed by single-crystal X-ray diffraction. The photophysical properties and related frontier orbital features of these compounds have been studied both experimentally and theoretically and demonstrate the dependence of the properties of the compounds on the position of substitution of the pyridyl moieties connecting to the pyrene core. It was found that the absorption spectra of 2- and 4-substituted pyrene derivatives display similar and weak influence on the S2 ← S0 excitations, whereas they are quite different from those of 1-substituted isomers. The emission spectra of 1- and 4-substituted pyrenes are quite similar, whereas those of 2-substituted isomers display the largest bathochromic shift. The 1,6-disubstituted compound 5 exhibits a near-unity emission quantum yield in solution, which is nearly three times higher than those of other regioisomeric dipyridyl-pyrenes. In addition, the tetrasubstituted 1,6-dipyridyl-3,8-di-n-butyl-pyrene (10) exhibits the highest solid-state quantum yield of 0.24 among all of the 10 pyridyl-pyrenes prepared in this study.