Peroxyoxalate chemiluminescence of N,N'-bistosyl-1H,4H-quinoxaline-2,3-dione and related compounds. Dependence on electronic nature of fluorophores

Jiro Motoyoshiya; Nobuaki Sakai; Minoru Imai; Yuka Yamaguchi; Ryu Koike; Yutaka Takaguchi; Hiromu Aoyama

doi:10.1021/jo011164g

Peroxyoxalate chemiluminescence of N,N'-bistosyl-1H,4H-quinoxaline-2,3-dione and related compounds. Dependence on electronic nature of fluorophores

J Org Chem. 2002 Oct 18;67(21):7314-8. doi: 10.1021/jo011164g.

Authors

Jiro Motoyoshiya¹, Nobuaki Sakai, Minoru Imai, Yuka Yamaguchi, Ryu Koike, Yutaka Takaguchi, Hiromu Aoyama

Affiliation

¹ Department of Chemistry, Faculty of Textile Science and Technology, Shinshu University, Ueda, Nagano 386-8567, Japan.

PMID: 12375960
DOI: 10.1021/jo011164g

Abstract

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 sigma(+) values and the relative singlet excitation yields in TsQD-CL enhanced by a series of fluorescent para,para'-disubstituted distyrylbenzenes.