title: Structural and photophysical properties of trianionic nine-coordinated near-IR emitting 8-hydroxyquinoline-based complexes.
abstract: Two building blocks, 2-(1H-tetrazol-5-yl)quinoline-8-ol (8-hydroxyquinoline-2-tetrazole) (H(2)hqt) and 8-hydroxyquinoline-2-carboxylic acid (H(2)hqa) provide convenient dianionic tridentate O,N,N- and O,N,O-chelating units containing the 8-hydroxyquinoline chromophore. These ligands form tris-chelate tris-anionic complexes [Ln(hqa)(3)]K(3) and [Ln(hqt)(3)]K(3) in water at pH = 12. At lower pH partially protonated species are formed. The Nd(III), Yb(III) and Er(III) complexes of hqa, and hqt and the partially protonated complex [Nd(H(1/2)hqa)(3)](2)(Et(3)NH)(3).Et(3)NHOTf have been crystallised from methanol solution. The X-ray crystal structure ([Nd(hqa)(3)]K(3).7MeOH(∞)·MeOH, [Er(hqa)(3)]K(3).4MeOH(∞)·3MeOH and [Nd(hqt)(3)]K(3).5MeOH(∞)·MeOH) show a helical arrangement of both ligands with an "anti" geometry for hqa and a "syn" geometry for hqt. Only tris-chelate complexes are formed in water and 0.04 M methanol solutions for both ligands. A "syn" geometry is found for the partially protonated dimeric complexes which is preserved in methanol solution. A statistical distribution of "anti" and "syn" species is found for [Ln(hqa)(3)]K(3) complexes in solution while the major solution geometry of [Ln(hqt)(3)]K(3) complexes is "syn". Sizable near-IR emission quantum yields were measured for the [Ln(hqa)(3)]K(3) complexes in solid state (0.06%, 0.18%, 0.0051% for Nd(III), Yb(III) and Er(III) respectively) and in methanol (0.063%, 0.28%, 0.0019% for Nd(III), Yb(III) and Er(III) respectively). All the values of quantum yields obtained for the hqt complexes are 5-17% higher than those measured for the hqa complexes. The trianionic complexes present a high solubility in organic and aqueous solvents and a good resistance to ligand dissociation compared to neutral tris 8-hydroxyquinoline complexes.
authors: CEA, INAC, Service de Chimie Inorganique et Biologique (UMR-E 3 CEA-UJF, FR 3200 CNRS), Laboratoire de Reconnaissance Ionique et Chimie de Coordination, CEA-Grenoble, 38054, Grenoble, Cedex 09, France.
authors: Gülay
authors: G
authors: Bozoklu
authors: Claire
authors: C
authors: Marchal
authors: Jacques
authors: J
authors: Pécaut
authors: Daniel
authors: D
authors: Imbert
authors: Marinella
authors: M
authors: Mazzanti
mesh_terms: D000838:Anions; D018360:Crystallography, X-Ray; D004871:Erbium / Q000737:chemistry; D006860:Hydrogen Bonding; D008027:Light; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009354:Neodymium / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D015125:Oxyquinoline / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D015018:Ytterbium / Q000737:chemistry
chemical_list: D000838:Anions; D009942:Organometallic Compounds; D009354:Neodymium; D015125:Oxyquinoline; D004871:Erbium; D015018:Ytterbium