RT info:eu-repo/semantics/article
T1 Fluorescent perylenylpyridine complexes: an experimental and theoretical study
A1 Expósito Fuertes, José Emilio
A1 Aullón, Gabriel
A1 Bardají Luna, Manuel
A1 Miguel García, Jesús Ángel
A1 Espinet Rubio, Pablo
K1 Perileno
K1 Perylene
AB The perylene derivative 2-(3-perylenyl)-4-methylpyridine (HPerPy) was prepared and used to synthesize [Ag(HPerPy)(PPh3)(OClO3)], with the perylene ligand bonded to the metal centre only by the pyridine nitrogen. The treatment of HPerPy with [Pd(OAc)2] in methanol or acetic acid led to acetate bridged dimers (μ-OOCCH3)2[Pd(PerPy)]2, six-membered or five-membered cycled at the perylenyl fragment. Substitution reactions afforded mononuclear compounds [Pd(PerPy)(acac)] (six-member or five-member cycled) and [Pd(PerPy)(S2COMe)] (six-member or five-member cycled). The reaction of HPerPy with a platinum(II) fragment led to a five-membered cyclometallated Pt(II) complex [Pt(PerPy)(acac)]. The oxidative addition with MeI gave the corresponding cyclometallated Pt(IV) compound [Pt(PerPy)(acac)MeI]. X-ray single crystal studies of compounds [Ag(HPerPy)(PPh3)(OClO3)], (μ-OOCCH3)2[Pd(PerPy)]2-five-membered, [Pd(PerPy)(acac)]-six-membered, [Pd(PerPy)(S2COMe)]-five-membered, [Pt(PerPy)(acac)]-five-membered, and [Pt(PerPy)(acac)MeI]-five-membered confirmed the proposed structures. The UV-Vis spectra show one intense absorption with vibronic coupling in the visible region with maxima in the range of 448–519 nm. DFT calculations were carried out for the absorption spectra of the HPerPy molecule and representative complexes [M(PerPy)(acac)] (M: Pd, Pt; five and six-membered isomers) and [Pt(PerPy)(acac)MeI], showing that the lowest energy most intense transition in the complexes corresponds to the HOMO → LUMO transition in the perylene moiety, although affected by the metallacycle size and the metal nature. All the compounds are fluorescent in solution, due to the perylene fragment. The emission spectra display maxima in the range of 468–549 nm, with quantum yields from 1.1 to 82%. The attenuation of the intensity of fluorescence by the presence of heavy atoms and the formation of metallacycles has been experimentally determined and sequenced.
PB Royal Society of Chemistry
SN 1477-9226
YR 2020
FD 2020
LK http://uvadoc.uva.es/handle/10324/42792
UL http://uvadoc.uva.es/handle/10324/42792
LA eng
NO Dalton Transactions, Issue 49, 2020, 13326-13338
NO Producción Científica
DS UVaDOC
RD 26-abr-2024