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Updated: Jun 24, 2026
Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Synthesis, structure, and optical properties of the platinum(II) complexes of indaphyrin and thiaindaphyrin
Kimberly S F Lau1, Shengxian Zhao, Claudia Ryppa
1Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700, USA.
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).
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