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dc.contributor.author
Wolcan, Ezequiel
dc.date.available
2021-08-03T17:21:44Z
dc.date.issued
2020-09
dc.identifier.citation
Wolcan, Ezequiel; Photosensitized generation of singlet oxygen from rhenium(I) complexes: A review; Elsevier Science SA; Inorganica Chimica Acta; 509; 119650; 9-2020; 1-11
dc.identifier.issn
0020-1693
dc.identifier.uri
http://hdl.handle.net/11336/137690
dc.description.abstract
I examine the photophysical properties for a number of thirty-eight Re(I) complexes in dilute solutions along with efficiencies of singlet oxygen production. Due to the structural differences around the Re(CO)3 core, the examples found in the literature of these efficient singlet oxygen photosensitizers can be divided into five categories: (I) tetracarbonyl Re(I) complexes bearing benzo[h]quinoline (bzq) and 1,10-phenanthroline (phen) ligands. (II) Re(CO)3 complexes of general formula LS-CO2-Re(CO)3(bpy) (LS = 2-pyrazine, 2-naphthalene, 9-anthracene, 1-pyrene, 2-anthraquinone) and XRe(CO)3L (X = CF3SO3, pyridine, Cl, norharmane; L = 2,2́-bipyridine (bpy), phen, Bathocuproinedisulfonate or dipyrido[3,2-a:2′,3′-c]phenazine (dppz)). (III) BrRe(CO)3L complexes where L is a pyridazine derivative. (IV) XRe(CO)3L complexes with X = P(Ph)3 and L = dipyrrinato derivative. (V) ClRe(CO)3L complexes where L = bpy derivatized with boron-dipyrromethene (BODIPY). Using these Re(I) complexes as photosensitizers, 1O2 (1Δg) can be efficiently produced either from non-emissive or from the highly emissive complexes. Depending on the nature of the Re(I) complex, the excited state responsible for the generation of singlet oxygen, via energy transfer to molecular oxygen, is either 3MLCT or a 3LC state. With LS-CO2-Re(CO)3(bpy) complexes, 1O2 (1Δg) is produced from oxygen quenching of 3LC states of anthracene and pyrene with high quantum yields (ΦΔ between 0.8 and 1.0). XRe(CO)3L complexes generate 1O2 (1Δg) mainly by oxygen quenching of their 3MLCT luminescence with an efficiency of 1O2 (1Δg) formation close to unity. Bimolecular rate constants for the quenching of the XRe(CO)3L complexes emission by molecular oxygen range between 1 and 2.5 × 109 M−1s−1. Complexes in (III) show ΦΔ values in dichloromethane which lie between 0.03 and 0.2, i.e. they are considerably lower than those of complexes in (I) and (II). In a series of rhenium dipyrrinates comprising a variety of aromatic substituents the phosphorescence lifetimes of the complexes are varied by the substituents in the micro-second order, and these long-lived triplet rhenium dipyrrinates are capable of sensitizing for efficient singlet oxygen generation (ΦΔ: 0.75–0.99). On the other hand, the trends observed across a series of rhenium complexes including the BODIPY ligand in their structure with respect to emission and 1O2 sensitization properties are rationalized in terms of the varied distal separation between the metal center and BODIPY groups in each system. It is suggested that the placement of the BODIPY group at the shortest possible distance to the metal center might be responsible, due to the enhanced ISC through a spin-orbit coupling, of the enhancement of ΦΔ.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Elsevier Science SA
dc.rights
info:eu-repo/semantics/restrictedAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Singlet Oxygen
dc.subject
Re(I) complexes
dc.subject
Photosensitized generation
dc.subject.classification
Físico-Química, Ciencia de los Polímeros, Electroquímica
dc.subject.classification
Ciencias Químicas
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
dc.title
Photosensitized generation of singlet oxygen from rhenium(I) complexes: A review
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2021-07-29T11:43:19Z
dc.journal.volume
509
dc.journal.number
119650
dc.journal.pagination
1-11
dc.journal.pais
Países Bajos
dc.journal.ciudad
Amsterdam
dc.description.fil
Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
dc.journal.title
Inorganica Chimica Acta
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1016/j.ica.2020.119650
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0020169320300943
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