RT info:eu-repo/semantics/article
T1 Higher fluorescence in platinum(IV) orthometallated complexes of perylene imine compared with their platinum(II) or palladium(II) analogues
A1 Expósito Fuertes, José Emilio
A1 Álvarez Paíno, Marta
A1 Aullón, Gabriel
A1 Miguel García, Jesús Ángel
A1 Espinet Rubio, Pablo
K1 Chemistry
AB The reaction of 3-perylenylmethylen-4'-ethylaniline () with [Pt2Me4(μ-SMe2)2] (and subsequent addition of PPh3) or with [Pt2(η(3)-C4H7)2(μ-Cl)2] produced cyclometallated Pt(II) complexes [Pt(C^N)Me(PPh3)] () and, respectively, [Pt2(C^N)2(μ-Cl)2] () (HC^N = 3-C20H11CH[double bond, length as m-dash]NC6H4-p-C2H5), with Pt bound to the ortho site of the perylenyl fragment. From the mononuclear complexes [Pt(C^N)L2] (L2 = acac (); S2COMe (); S2CNEt2 () are easily formed. Oxidative addition of methyl iodide to the square-planar Pt(II) complexes , , and gave the corresponding cyclometallated Pt(IV) compounds [Pt(C^N)L2MeI] , and . The X-ray structures of , , and show that the perylenyl fragment remains essentially flat in and and slightly twisted in . Comparison of the optical properties of these Pt(II) complexes with those reported for similar Pd(II) derivatives reveals that the change of metal exerts a notable influence on the UV-vis spectra. In solution at room temperature, all the Pt complexes exhibit fluorescence associated with the perylene fragment with low emission quantum yields for the Pt(II) complexes (<1%) and remarkably higher emission values for the Pt(IV) complexes: up to 29%, with emission lifetimes of 1-5 ns. Time-dependent density functional theory (TD-DFT) calculations were performed on the perylene imine and on representative complexes [M(C^N)(acac)] (M = Pd, Pt) and [Pt(C^N)(acac)MeI] to analyse the absorption spectra. These calculations support a perylene-dominated intraligand π-π*emissive state based on the HOMO and LUMO orbitals of the perylene chromophore, and a ligand-to-ligand charge-transfer (more intense for the Pt(II) complex) that explains the observed influence of the metal on the absorption properties.
PB Royal Society of Chemistry
SN 1477-9226
YR 2015
FD 2015
LK http://uvadoc.uva.es/handle/10324/21768
UL http://uvadoc.uva.es/handle/10324/21768
LA eng
NO Dalton Transactions, 2015,44, p. 16164-16176
NO Producción Científica
DS UVaDOC
RD 27-dic-2024