Peroxyoxalate Chemiluminescence of N,N‘-Bistosyl-1H,4H-quinoxaline-2,3-dione and Related Compounds. Dependence on Electronic Nature of Fluorophores

• Published in: Journal of organic chemistry 2002-10, Vol.67 (21), p.7314-7318
• Main Authors: Motoyoshiya, Jiro, Sakai, Nobuaki, Imai, Minoru, Yamaguchi, Yuka, Koike, Ryu, Takaguchi, Yutaka, Aoyama, Hiromu
• Format: Article
• Language: English
• Subjects: Chemiluminescence; Chemistry; Exact sciences and technology; General and physical chemistry
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo011164g

The title compound N,N‘-bistosyl-1H,4H-quinoxaline-2,3-dione (TsQD) provides peroxyoxalate chemiluminescence (PO-CL) when reacted with hydrogen peroxide in the presence of fluorophores. The chemiluminescence (CL) efficiency of TsQD was superior to that of other related compounds such as bis(2,4,6-trichlorophenyl) oxalate (TCPO), a typical oxalate for the peroxyoxalate PO-CL, under an aqueous condition. Factors affecting the PO-CL efficiency are discussed from the viewpoint of the structures of the substrates and the electronic nature of the fluorophores. A linear correlation of the logarithmic values evaluated from the CL quantum yields with the oxidation potentials of the aromatic fluorophores supports the involvement of the chemically initiated electron exchange luminescence (CIEEL) mechanism in both TsQD- and TCPO-CL systems. Also, an excellent Hammett relationship was derived from the correlation between the σ+ values and the relative singlet excitation yields in TsQD-CL enhanced by a series of fluorescent para,para‘-disubstituted distyrylbenzenes.