Reactivity of Cationic Lanthanide(III) Monoporphyrinates towards Anionic Cyanometallates – Preparation, Crystal Structure, and Luminescence Properties of Cyanido‐Bridged Di‐ and Trinuclear d–f Complexes

The metathesis reaction between two equivalents of [Ln(tpp)(H 2 O) 3 ]Cl (Ln = Yb, Er; tpp 2– = tetraphenylporphyrinate dianion) and one equivalent of cyanometallate in dmf at room temperature under nitrogen for 24 hours gave the cyanido‐bridged d–f trinuclear complexes [{Ln(tpp)(dmf) n } 2 {(μ‐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 }{(μ‐NC) 2 Fe(CN) 4 }{Er(Htpp)(dmf) 2 }] ( 5 ), and a dinuclear complex [{Er(tpp)(dmf)(H 2 O)}(μ‐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 X‐ray 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 π→π* 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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)