Reactivity of cationic lanthanide(III) monoporphyrinates towards anionic cyanometallates - Preparation, crystal structure, and luminescence properties of cyanido-bridged di- and trinuclear d-f complexes

摘要

The metathesis reaction between two equivalents of [Ln(tpp)(H2O)(3)]Cl (Ln = Yb, Er; tpp(2) = tetraphenylporphyrinate dianion) and one equivalent of cyanometallate in dmf atd room temperature under nitrogen for 24 hours gave the cyanido-bridged d-f trinuclear complexes [{Ln(tpp)(dmf)(n)}(2){mu-NC)(2)M(CN)(2)}] (Ln = Yb, n = 2, M = Ni, 1; Ln = Er, n = 3, M = Ni, 2; Ln = Yb, n = 2, M = Pt, 3; Ln = Er, n = 3, M = Pt, 4), a trinuclear complex [{Er(tpp)(dmf)(2){[mu-NC)(2)Fe(CN)(4)}{Er(Htpp)(dmf)(2)}] (5), and a dinuclear complex [{Er(tpp)(dmf)(H2O)}((mu-NC)Ag(CN)] (6) when the cyanometallate used was the dianion [M(CN)(4)](2-) (M = Ni, Pt), the trianion [Fe(CN)(6)](3), and monoanion [Ag(CN)(2)](-), respectively. The solid-state structures of these complexes were ascertained by Xray crystallography. Photoluminescence studies of complexes 1-4 showed that these complexes displayed photophysical properties characteristic of normal metal-porphyrinato complexes. Their absorption bands and emission peaks in the visible region are typical of the intraligand pi ->pi* transitions of the porphyrinato ligand. Furthermore, these complexes also exhibited emission characteristic of the lanthanide(III) ion in the near-infrared (NIR) region, which was quenched by the cyanometallates. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).