title: Synthesis, structure, and optical properties of the platinum(II) complexes of indaphyrin and thiaindaphyrin.
abstract: The novel free base meso-di(5'-methylthien-2'-yl)thiaindaphyrin, 10, was prepared from the corresponding meso-tetra(thien-2-yl)porphyrin using a methodology analogous to that for the preparation of known meso-diphenylindaphyrin, 5: beta,beta'-Dihydroxylation of the porphyrin is followed by oxidative diol cleavage. The resulting aldehyde moieties undergo an acid-catalyzed intramolecular Friedel-Crafts alkylation of the adjacent meso-thienyl groups with concomitant oxidation. Insertion of Pt(II) into either of the chromophores is facile, producing 5Pt and 10Pt. The crystal structure of 5Pt, the first for any indaphyrin, shows that the conformation of the indaphyrinato ligand is strongly ruffled, while the N(4) donor set that coordinates the central Pt(II) maintains a near-perfect square-planar coordination geometry around the central metal ion (crystal data for C(44)H(24)N(4)O(2)Pt: triclinic space group P1 with a = 8.8735(4) A, b = 12.9285(6) A, c = 14.3297(6) A, alpha = 88.785(1) degrees, beta = 82.248(1) degrees, gamma = 72.422(1) degrees; Z = 2). The UV-vis and emission spectra, triplet yields, and lifetimes of the Pt(II) complexes 5Pt and 10Pt were determined. Both complexes luminesce (in EtOH at 77 K) in the NIR (5Pt: lambda(max-emission) = 864, 974 nm, lifetime 2 micros; 10Pt: lambda(max-emission) = 990, 1112, 1276 nm) with modest to low quantum yields (Phi(p) approximately 1% and approximately 6 x 10(-3) %, respectively).
authors.affiliation: Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700, USA.
authors.forename: Kimberly S F
authors.initials: KS
authors.lastname: Lau
authors.forename: Shengxian
authors.initials: S
authors.lastname: Zhao
authors.forename: Claudia
authors.initials: C
authors.lastname: Ryppa
authors.forename: Steffen
authors.initials: S
authors.lastname: Jockusch
authors.forename: Nicholas J
authors.initials: NJ
authors.lastname: Turro
authors.forename: Matthias
authors.initials: M
authors.lastname: Zeller
authors.forename: Martin
authors.initials: M
authors.lastname: Gouterman
authors.forename: Gamal E
authors.initials: GE
authors.lastname: Khalil
authors.forename: Christian
authors.initials: C
authors.lastname: Brückner