Photoisomerization Mechanism of Ruthenium Sulfoxide Complexes: Role of the Metal-Centered Excited State in the Bond Rupture and Bond Construction Processes.
Chemistry
; 22(40): 14285-92, 2016 Sep 26.
Article
em En
| MEDLINE
| ID: mdl-27553700
ABSTRACT
Phototriggered intramolecular isomerization in a series of ruthenium sulfoxide complexes, [Ru(L)(tpy)(DMSO)](n+) (where tpy=2,2'6',2''-terpyridine; DMSO=dimethyl sulfoxide; L=2,2'-bipyridine (bpy), n=2; N,N,N',N'-tetramethylethylenediamine (tmen) n=2; picolinate (pic), n=1; acetylacetonate (acac), n=1; oxalate (ox), n=0; malonate (mal), n=0), was investigated theoretically. It is observed that the metal-centered ligand field ((3) MC) state plays an important role in the excited state SâO isomerization of the coordinated DMSO ligand. If the population of (3) MCS state is thermally accessible and no (3) MCO can be populated from this state, photoisomerization will be turned off because the (3) MCS excited state is expected to lead to fast radiationless decay back to the original (1) GSS ground state or photodecomposition along the Ru(2+) -S stretching coordinate. On the contrary, if the population of (3) MCS (or (3) MCO ) state is inaccessible, photoinduced SâO isomerization can proceed adiabatically on the potential energy surface of the metal-to-ligand charge transfer excited states ((3) MLCTS â(3) MLCTO ). It is hoped that these results can provide valuable information for the excited state isomerization in photochromic d(6) transition-metal complexes, which is both experimentally and intellectually challenging as a field of study.
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Base de dados:
MEDLINE
Idioma:
En
Revista:
Chemistry
Assunto da revista:
QUIMICA
Ano de publicação:
2016
Tipo de documento:
Article