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Synthesis and Coordination Chemistry of Ligands for Supramolecular Chemistry and Sensing Applications

Clayton, Hayley J. (2008) Synthesis and Coordination Chemistry of Ligands for Supramolecular Chemistry and Sensing Applications. Doctoral thesis, University of Huddersfield.

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    Abstract

    A series of multidentate N-donor ligands have been synthesised all containing pyridyl
    and pyridyl/thiazole units and their coordination behaviour is described.
    The ligands are classified into four types; i) terpyridine containing pyridyl/thiazole
    ligands (L1-3); ii) pyridyl/thiazole ligands containing a 3,3′-disubstituted bipyridine
    core. (L4-8); iii) 2,2′-bipyridine containing a crown ether moiety (L9-11); and iv) a 2,2′-
    bipyridine derived ligand containing a urea functional group in the 3,3′-positions
    (L12).

    Chapter II describes terpyridyl/pyridyl/thiazole ligands: - the synthesis of (L1-3) is
    described and the complexes ([Cu(L1)][ClO4]2, [Ni(L2)][ClO4]2, [Co(L2)][ClO4]2,
    [Cd3(L3)2][ClO4]6) structurally characterised. Partitioning of the ligands (L1-3) is
    dependant on the position of the thiazole ring within the ligand chain. This
    partitioning is found to occur at a position adjacent to that of the thiazole ring in all
    but the L2 ligand complexes, where it is partitioned preferentially at a position
    creating favourable coordination geometry for the metal ion.

    Chapter III describes 3,3′-disubstituted pyridyl/thiazole ligands (L4-8): - the novel
    potentially hexadentate ligands (L4, 5), the potentially octadentate ligand (L6) and the
    potentially tetradentate ligands (L7, 8) have been synthesized and structurally
    characterised. All ligands are found to partition at the central pyridine unit due to
    unfavourable steric interactions to form a pyridyl/thiazole/pyridyl-binding domain
    (L4-6) and the pyridyl/thiazole-binding domain (L7,8). The substituents are found to
    dominate the control of the formation of complexes produced ([Zn(L4)][ClO4]2,
    [Cd(L5)][ClO4]2, [Cd2(L6)2][ClO4]2, [Cd2(L8)2][ClO4]2).

    Chapter IV, Section 1 describes ditopic bipyridine/crown ether ligands: - the synthesis
    of (L9-11) is described and the Ru (II) complexes (L9-11) structurally characterised. The
    Ru(II) complexes of these 3,3′-disubstituted crown ether species were found to
    luminesce. Modulation of the luminescent properties of the ruthenium complex was
    investigated with a selection of common cations but resulted in little or no response.

    Chapter IV: - Section 2- Ditopic bipyridine/urea ligands: - the novel ligand containing
    urea substituent side chains (L12) has been synthesised and a ligand containing both
    pyridine and urea substituents has been synthesised and characterised.

    A ruthenium complex (X) was synthesised with ligand (L12) and (bipy)2RuCl2, the
    resulting structure confirmed via 1H & 13C NMR as well as electrospray mass
    spectrometry (ESI-MS). Unfortunately no complexes have been structurally
    characterised due to the instability and decomposition of the complex after a short
    period of time. The ruthenium complex however was found to luminesce;
    ligand/anion recognition studies with complex (X) and a selection of common anions
    showed a marked change, a ten fold increase in the luminescence was observed with
    the addition of H2PO4
    - when in a non-aqueous solvent.

    Item Type: Thesis (Doctoral)
    Subjects: Q Science > Q Science (General)
    Q Science > QD Chemistry
    Schools: School of Applied Sciences
    Depositing User: Pat Whitworth
    Date Deposited: 16 Feb 2010 11:42
    Last Modified: 28 Jul 2010 19:53
    URI: http://eprints.hud.ac.uk/id/eprint/6954

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