title: Peripherally metalated secoporphyrazines: a new generation of photoactive pigments.
abstract: Base-catalyzed cross condensation of dipropylmaleonitrile 1 with bis(dimethylamino)maleonitrile 2 in an equimolar ratio afforded the porphyrazines 3a, 4a, 5a, 6a and 7a. Subsequent demetalation of 5a with TFA followed by remetalation with Zn(OAc)(2) gave ligand 5c in good yield. Compound 5c was, in turn, selectively oxidized and further peripherally functionalized using Pt(PhCN)(2)Cl(2) and PdCl(2) to yield the novel seco solitaire porphyrazines 10a and 10b. The photophysical profiles of the seco solitaire porphyrazines 10a and 10b were evaluated by means of absorption, emission, and transient absorption spectroscopy. The new pigments 10a and 10b were found to be photochemically more stable than the solitaire complexes 3d and 3e and mediated the generation of singlet oxygen with quantum yields of 0.59 and 0.45, respectively.
authors.affiliation: Departments of Chemistry, Imperial College of Science, Technology and Medicine, South Kensington, London, SW7 2AY, U.K.
authors.forename: Efstathia G
authors.initials: EG
authors.lastname: Sakellariou
authors.forename: Antonio Garrido
authors.initials: AG
authors.lastname: Montalban
authors.forename: Hubert G
authors.initials: HG
authors.lastname: Meunier
authors.forename: Garry
authors.initials: G
authors.lastname: Rumbles
authors.forename: David
authors.initials: D
authors.lastname: Phillips
authors.forename: Richard B
authors.initials: RB
authors.lastname: Ostler
authors.forename: Klaus
authors.initials: K
authors.lastname: Suhling
authors.forename: Anthony G M
authors.initials: AG
authors.lastname: Barrett
authors.forename: Brian M
authors.initials: BM
authors.lastname: Hoffman