The Hammett correlation between distyrylbenzene substituents and chemiluminescence efficiency providing various ρ-values for peroxyoxalate chemiluminescence of several oxalates

Abstract

Peroxyoxalate chemiluminescence (PO-CL) was investigated using eight oxalates with various phenol moieties and the distyrylbenzene (DSB) fluorophores with various substituents. The ρ-values in the Hammett correlation between the substituent constants (σ p + ) of the DSBs and the singlet chemiexcitation yields (Φ S ) for the PO-CL reactions varied from -0.50 to -1.01 depending on the oxalate structure, and the reactive oxalates tended to afford the higher absolute ρ-values but with a few exceptions. Based on the CIEEL mechanism, these experimental observations suggest that the aryloxy groups still remain in the 1,2-dioxetanones (DOTs), which are the postulated high-energy intermediates, and control the electronic properties of DOTs as electron-acceptors. The LUMO energies of the DOTs calculated by the ab initio method with a B3LYP/6-31g(d) basis set reveal that the lower the DOT-LUMO energies, the higher the absolute ρ-values were provided for the corresponding oxalates, as predicted by the frontier molecular orbital (FMO) theory. Thus, the chemical species interacting with the DSBs would be not unitary and will be DOTs.2

All Eyes on Visible‐Light Peroxyoxalate Chemiluminescence Read‐Out Systems

“…Only bis(2,6-dichlorophenyl) oxalate and bis(2,4,6-trichlorophenyl) oxalate exhibited deviations from the general trend reported, which can be attributed to the para-substitution and its steric hindrance. [18] Thus, in agreement with Aoyama, [17b] Murayamae tal. proposed aryloxy-sub-stituted1 ,2-dioxetanones 4b as the HEI.…”

“…They described a linear dependency of the ρ ‐values and the p K a values of the corresponding phenols correlating to the observed CL decay rates. Only bis(2,6‐dichlorophenyl) oxalate and bis(2,4,6‐trichlorophenyl) oxalate exhibited deviations from the general trend reported, which can be attributed to the para ‐substitution and its steric hindrance . Thus, in agreement with Aoyama, Murayama et al.…”

Rapid and simple G-quadruplex DNA aptasensor with guanine chemiluminescence detection

“…Fig. The possible CRET mechanism in guanine chemiluminescence reaction may be similar to chemically initiated electron exchange luminescence (CIEEL) mechanism of peroxyoxalate chemiluminescence (Lee et al, 2002a(Lee et al, , 2002bMaruyama et al, 2013;Park et al, 2011). The ratio determined with 100 s measurement was the smallest.…”

Intraparticle Energy Level Alignment of Semiconducting Polymer Nanoparticles to Amplify Chemiluminescence for Ultrasensitive In Vivo Imaging of Reactive Oxygen Species

“…Accordingly, the key step of the CIEEL that determines the chemiluminescence efficiency of SPNs is the intermolecular electron transfer from the SP to 1,2-dioxetanedione. 32 The degree of freedom for such an intermolecular electron transfer process can be qualitatively evaluated according to the energy interval between the highest occupied molecular orbital (HOMO) of SP and the lowest unoccupied molecular orbital (LUMO) of 1,2-dioxetanedione. Among these SPNs, the HOMO of PFPV is the closest to the LUMO of 1,2-dioxetanedione (Figure 3b), and thus the intermolecular electron transfer between them is most facilitated, leading to the highest chemiluminescence QY.…”