Naslov
The effect of the rate of photoinduced electron transfer on the photodecarboxylation efficiency in phthalimide photochemistry

Autori
Mandić, Leo ; Sohora, Margareta ; Mihaljević, Branka ; Biczók, László ; Basarić, Nikola

Izvornik
Journal of photochemistry and photobiology. A, Chemistry (1010-6030) 408 (2021); 113109, 7

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
laser flash photolysis ; peptides ; photoinduced electron transfer ; phthalimides

Sažetak
Reactivity in photoinduced electron transfer reactions (PET) has been investigated in a series of molecules possessing different distances between the electron donor (carboxylate or alkoxyphenyl) and the phthalimide as the electron acceptor. The molecules were strategically designed to separate the donor and the acceptor by a rigid adamantane spacer or through a peptide backbone with different number of amino acid residues. PET was investigated by laser flash photolysis (LFP). Although previous reports demonstrated that the quantum yields of the photodecarboxylation reaction (ΦR) depend on the distance between the donor and acceptor moieties, the measured lifetimes of the triplet excited state did not provide information on the rates of PET. Due to reversible PET and back electron transfer processes in compounds 1-5, the measured lifetimes correspond to the sum of the rate constants for the disappearance of the charge transfer species. In the series of peptides, three different PET processes take place and LFP provided rate constant for the reactions occurring subsequent to the intrastrand PET between the carboxylate and the alkoxyphenyl radical cation. The understanding of the factors that affect intramolecular PET processes is important for the rational design of different applications.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA