Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Shunichi Fukuzumi | * |
dc.contributor.author | 정지은 | * |
dc.date.accessioned | 2021-01-14T16:30:14Z | - |
dc.date.available | 2021-01-14T16:30:14Z | - |
dc.date.issued | 2020 | * |
dc.identifier.issn | 1477-9226 | * |
dc.identifier.other | OAK-28586 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/255948 | - |
dc.description.abstract | A RuII complex, [RuII(tpphz)(bpy)2]2+ (1) (tpphz = tetrapyridophenazine, bpy = 2,2′-bipyridine), whose tpphz ligand has a pyrazine moiety, is converted efficiently to [RuII(tpphz-HH)(bpy)2]2+ (2) having a dihydropyrazine moiety upon photoirradiation of a water-methanol mixed solvent solution of 1 in the presence of an electron donor. In this reaction, the triplet metal-to-ligand charge-transfer excited state (3MLCT∗) of 1 is firstly formed upon photoirradiation and the 3MLCT∗ state is reductively quenched with an electron donor to afford [RuII(tpphz-)(bpy)2]+, which is converted to 2 without the observation of detectable reduced intermediates by nano-second laser flash photolysis. The inverse kinetic isotope effect (KIE) was observed to be 0.63 in the N-H bond formation of 2 at the dihydropyrazine moiety. White-light (380-670 nm) irradiation of a solution of 1 in a protic solvent, in the presence of an electron donor under an inert atmosphere, led to photocatalytic H2 evolution and the hydrogenation of organic substrates. In the reactions, complex 2 is required to be excited to form its 3MLCT∗ state to react with a proton and aldehydes. In photocatalytic H2 evolution, the H-H bond formation between photoexcited 2 and a proton is involved in the rate-determining step with normal KIE being 5.2 on H2 evolving rates. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations on the reaction mechanism of H2 evolution from the ground and photo-excited states of 2 were performed to have a better understanding of the photocatalytic processes. © 2020 The Royal Society of Chemistry. | * |
dc.language | English | * |
dc.publisher | Royal Society of Chemistry | * |
dc.title | Photocatalytic hydrogen evolution using a Ru(ii)-bound heteroaromatic ligand as a reactive site | * |
dc.type | Article | * |
dc.relation.issue | 47 | * |
dc.relation.volume | 49 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 17230 | * |
dc.relation.lastpage | 17242 | * |
dc.relation.journaltitle | Dalton Transactions | * |
dc.identifier.doi | 10.1039/d0dt03546g | * |
dc.identifier.wosid | WOS:000599093600021 | * |
dc.identifier.scopusid | 2-s2.0-85098078957 | * |
dc.author.google | Sawaki T. | * |
dc.author.google | Ishizuka T. | * |
dc.author.google | Namura N. | * |
dc.author.google | Hong D. | * |
dc.author.google | Miyanishi M. | * |
dc.author.google | Shiota Y. | * |
dc.author.google | Kotani H. | * |
dc.author.google | Yoshizawa K. | * |
dc.author.google | Jung J. | * |
dc.author.google | Fukuzumi S. | * |
dc.author.google | Kojima T. | * |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | * |
dc.contributor.scopusid | 정지은(55320529400) | * |
dc.date.modifydate | 20240401081001 | * |