TY - JOUR
T1 - Efficient catalysis of rare-earth metal ions in photoinduced electron-transfer oxidation of benzyl alcohols by a flavin analogue
AU - Fukuzumi, Shunichi
AU - Yasui, Kiyomi
AU - Suenobu, Tomoyoshi
AU - Ohkubo, Kei
AU - Fujitsuka, Mamoru
AU - Ito, Osamu
PY - 2001/11/22
Y1 - 2001/11/22
N2 - A flavin analogue (riboflavin-2′,3′,4′,5′-tetraacetate, Fl) forms the 1:1 and 1:2 complexes with rare-earth metal ions. The largest formation constants K1 and K2 for the 1:1 and 1:2 complexes between Fl and Sc3+ are determined as K1 = 3.1 × 104 M-1 and K2 = 1.4 × 103 M-1, respectively. The complexation of Fl with rare-earth metal ions results in blue shifts of the fluorescence maximum, shortening of the fluorescence lifetime, and more importantly the change in the lowest excited state from the n,π* triplet state of Fl to the π,π* singlet states of Fl-rare-earth metal ion complexes as indicated by the disappearance of the triplet-triplet (T-T) absorption spectrum of Fl by the complexation with metal ions. The strong complex formation between Fl and rare-earth metal ions enhances the oxidizing ability of the excited state of Fl as indicated by the significant acceleration in the fluorescence quenching rates of Fl-rare earth metal ion complexes via electron transfer from electron donors (e.g., alkylbenzenes) as compared to those of uncomplexed Fl. The one-electron reduction potential of the singlet excited state of the 1:2 complex between Fl and Sc3+, 1(Fl-2Sc3+)* (* denotes the excited state), is positively shifted by 780 mV as compared to 1Fl*. Such a remarkable enhancement of the redox reactivity of 1(Fl-2Sc3+)* as compared to that of 1Fl* makes it possible to oxidize efficiently p-chlorobenzyl alcohol to p-chlorobenzaldehyde by 1(Fl-2Sc3+)*, although no photooxidation of p-chlorobenzyl alcohol by Fl occurred in deaerated MeCN. The quantum yield for the photooxidation of p-chlorobenzyl alcohol by Fl-2Sc3+ is the largest among various Fl-metal ion complexes. A comparison of the observed rate constant derived from the dependence of the quantum yield on the concentration of p-chlorobenzyl alcohol with the fluorescence quenching rate constant by electron transfer from the alcohol and the direct detection of radical intermediates reveal that the photooxidation proceeds via electron transfer from p-chlorobenzyl alcohol to 1(Fl-2Sc3+)*. Under an atmospheric pressure of oxygen, the photooxidation of p-methoxybenzyl alcohol by oxygen proceeds efficiently in the presence of Fl-Lu3+ which acts as an efficient photocatalyst. No photodegradation was observed in the case of the Fl-Lu3+ complex, whereas the facile photodegradation of Fl-Mg2+ has precluded the efficient photocatalytic oxidation of the alcohol by oxygen.
AB - A flavin analogue (riboflavin-2′,3′,4′,5′-tetraacetate, Fl) forms the 1:1 and 1:2 complexes with rare-earth metal ions. The largest formation constants K1 and K2 for the 1:1 and 1:2 complexes between Fl and Sc3+ are determined as K1 = 3.1 × 104 M-1 and K2 = 1.4 × 103 M-1, respectively. The complexation of Fl with rare-earth metal ions results in blue shifts of the fluorescence maximum, shortening of the fluorescence lifetime, and more importantly the change in the lowest excited state from the n,π* triplet state of Fl to the π,π* singlet states of Fl-rare-earth metal ion complexes as indicated by the disappearance of the triplet-triplet (T-T) absorption spectrum of Fl by the complexation with metal ions. The strong complex formation between Fl and rare-earth metal ions enhances the oxidizing ability of the excited state of Fl as indicated by the significant acceleration in the fluorescence quenching rates of Fl-rare earth metal ion complexes via electron transfer from electron donors (e.g., alkylbenzenes) as compared to those of uncomplexed Fl. The one-electron reduction potential of the singlet excited state of the 1:2 complex between Fl and Sc3+, 1(Fl-2Sc3+)* (* denotes the excited state), is positively shifted by 780 mV as compared to 1Fl*. Such a remarkable enhancement of the redox reactivity of 1(Fl-2Sc3+)* as compared to that of 1Fl* makes it possible to oxidize efficiently p-chlorobenzyl alcohol to p-chlorobenzaldehyde by 1(Fl-2Sc3+)*, although no photooxidation of p-chlorobenzyl alcohol by Fl occurred in deaerated MeCN. The quantum yield for the photooxidation of p-chlorobenzyl alcohol by Fl-2Sc3+ is the largest among various Fl-metal ion complexes. A comparison of the observed rate constant derived from the dependence of the quantum yield on the concentration of p-chlorobenzyl alcohol with the fluorescence quenching rate constant by electron transfer from the alcohol and the direct detection of radical intermediates reveal that the photooxidation proceeds via electron transfer from p-chlorobenzyl alcohol to 1(Fl-2Sc3+)*. Under an atmospheric pressure of oxygen, the photooxidation of p-methoxybenzyl alcohol by oxygen proceeds efficiently in the presence of Fl-Lu3+ which acts as an efficient photocatalyst. No photodegradation was observed in the case of the Fl-Lu3+ complex, whereas the facile photodegradation of Fl-Mg2+ has precluded the efficient photocatalytic oxidation of the alcohol by oxygen.
UR - http://www.scopus.com/inward/record.url?scp=0035936241&partnerID=8YFLogxK
U2 - 10.1021/jp012709d
DO - 10.1021/jp012709d
M3 - Article
AN - SCOPUS:0035936241
SN - 1089-5639
VL - 105
SP - 10501
EP - 10510
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 46
ER -