The matrix isolation technique has been combined with Vis/UV spectroscopy to characterize electronic transitions in 1:1 complexes of OVCl3 with a series of lone pair electron donors. Two unstructured absorptions between 400 and 600 nm were observed for each complex, and assigned to intermolecular ligand-to-metal charge transfer transitions. Qualitative agreement between the positions of the two charge transfer bands and the IP for the donor was observed. These charge transfer bands were identified as the photoactive transitions in the subsequent photochemistry of these complexes. Theoretical DFT calculations support the identification of these molecular complexes. (C) 2004 Elsevier B.V. All rights reserved.