Artículo
Two-Photon Chemistry in Ruthenium 2,2’-Bipyridyl-Functionalized SingleWall Carbon Nanotubes
Martín, Roberto; Jimenez, Liliana Beatriz
; Alvaro, Mercedes; Scaiano, Juan Cesar; Garcia, Hermenegildo
![Icon](/themes/CONICETDigital/images/conicet.png)
Fecha de publicación:
21/06/2010
Editorial:
Wiley VCH Verlag
Revista:
Chemistry- A European Journal
ISSN:
0947-6539
e-ISSN:
1521-3765
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
Ruthenium polypyridyl complexes are widely used as light harvesters in dye-sensitized solar cells. Since one of the potential applications of single-wall carbon nanotubes (SWCNTs) and their derived materials is their use as active components in organic and hybrid solar cells, the study of the photochemistry of SWCNTs with tethered ruthenium polypyridyl complexes is important. A water-soluble ruthenium tris(bipyridyl) complex linked through peptidic bonds to SWCNTs (Ru-SWCNTs) was prepared by radical addition of thiol-terminated SWCNT to a terminal C=C double bond of a bipyridyl ligand of the ruthenium tris(bipyridyl) complex. The resulting macromolecular Ru-SWCNT (≈500nm, 15.6% ruthenium complex content) was water-soluble and was characterized by using TEM, thermogravimetric analysis, chemical analysis, and optical spectroscopy. The emission of Ru-SWCNT is 1.6 times weaker than that of a mixture of [Ru(bpy)3]2+ and SWCNT of similar concentration. Time-resolved absorption optical spectroscopy allows the detection of the [Ru(bpy)3]2,+-excited triplet and [Ru(bpy)3]+. The laser flash studies reveal that Ru-SWCNT exhibits an unprecedented two-photon process that is enabled by the semiconducting properties of the SWCNT. Thus, the effect of the excitation wavelength and laser power on the transient spectra indicate that upon excitation of two [Ru(bpy)3]2+ complexes of Ru-SWCNT, a disproportionation process occurs leading to delayed formation of [Ru(bpy) 3]+ and the performance of the SWCNT as a semiconductor. This two-photon delayed [Ru(bpy)3]+ generation is not observed in the photolysis of [Ru(bpy)3]3+; SWCNT acts as an electron wire or electron relay in the disproportionation of two [Ru(bpy)3]2+ triplets in a process that illustrates that the SWCNT plays a key role in the process. We propose a mechanism for this two-photon disproportionation compatible with i) the need for high laser flux, ii) the long lifetime of the [Ru(bpy)3]2+ triplets, iii) the semiconducting properties of the SWNT, and iv) the energy of the HOMO/LUMO levels involved.
Archivos asociados
Licencia
Identificadores
Colecciones
Articulos(INFIQC)
Articulos de INST.DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Articulos de INST.DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Citación
Martín, Roberto; Jimenez, Liliana Beatriz; Alvaro, Mercedes; Scaiano, Juan Cesar; Garcia, Hermenegildo; Two-Photon Chemistry in Ruthenium 2,2’-Bipyridyl-Functionalized SingleWall Carbon Nanotubes; Wiley VCH Verlag; Chemistry- A European Journal; 16; 24; 21-6-2010; 7282-7292
Compartir
Altmétricas