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Crown Ether Encapsulation Effects on the Optical Properties of Delocalized and Partially Localized Bridged Ruthenium
Alessandro Ferretti1, Alessandro Lami, Giovanni Villani
1Istituto di Chimica Quantistica ed Energetica Molecolare del CNR, Via Risorgimento 35, I-56126 Pisa, Italy.
Abstract:
The effects of crown ether encapsulation on the position of the near-IR-vis bands of [(NH(3))(5)Ru-pyz-Ru(NH(3))(5)](m)()(+) and [(NH(3))(5)Ru-(4,4'-bpy)-Ru(NH(3))(5)](m)()(+) (m = 4, 5) have been investigated within a purely electronic picture. The model accounts for the observed behavior and furnishes a theoretical explanation. The near-IR band, observed experimentally around 1 eV, is found to be a metal-to-ligand charge-transfer transition, in contrast to the common idea that ascribes it to an intervalence transition (Ferretti, A.; Lami, A.; Villani, G. Inorg. Chem. 1998, 37, 2799). The results obtained are a further confirmation that the model proposed contains all the essential ingredients for a basic minimal description of electron transfer in donor-bridge-acceptor systems.