Novel multifunctional N,O,S - donor ligands for d- and f-element complexation 22.02.2012Juliane März.

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Presentation transcript:

Novel multifunctional N,O,S - donor ligands for d- and f-element complexation Juliane März

TU Dresden Department of Chemistry and Food Chemistry 1 Introduction

Basic research in energy and in nuclear safety and disposal Coordination Chemistry of d- and f-block elements University of Leipzig TU Dresden HZDR 02NUK014A Joint research project: Novel multifunctional N,O,S - donor ligands for d- and f-element complexation 1 Introduction

Members of our group and their fields of research Porphyrines Schiff bases β -Diketones/ Hydrazones Amides Schiff bases 1 Introduction

Ligand systems Schiff basesβ-DiketonesDiamidesAmines Synthesis and characterisation Characteristics of complexation - Spectroscopy: ESI-MS, NMR, IR, UV/Vis, Fluorescence - X-ray analysis - Potentiometry - Liquid-liquid extraction 1 Introduction Hydrazones

β-Diketones Coordination of Eu(III): [Eu(L) 3 (H 2 O) 2 ]·THF 2 Results O 2 donor set CN = 8 Complex Synthesis: - THF - Deprotonation agent Na 2 CO 3

Hydazones 2 Results Coordination of UO 2 2+ : (Et 3 NH) 2 [(UO 2 ) 2 (μ-O 2 )(L) 2 ] MeOH Complex Synthesis: - MeOH - Deprotonation agent Et 3 N N 2 O 2 donor set CN = 8

U1 N9 O10 O16 Schiff Bases Microwave synthesis of the complex Coordination of UO 2 2+ : [UO 2 (L)] 2 Results N 2 O 3 donor set CN = 7

N,N,N-Tris(2-picolyl)methane tricarboxamide Left-handed triple N H … O hydrogen bond helix Amides 2 Results X-ray analysis

UV/Vis Spectroscopy: Fe(III) Job Plot at 660 nm: 2:1 ratio (L:Fe 3+ ) Fe(NO 3 ) 3 ·6H 2 O, c total = 2.5·10 -4 M in MeOH 2 Results

UV/Vis Spectroscopy : La(III) La(NO 3 ) 3 ·6H 2 O Preparation of the samples: M in THF 1 h heating c total = 4·10 -3 M in MeOH 2 Results

Gd(III)-complex of L1 Luminescence of Ln(III)- complexes in THF, H 2 O and EtOH/H 2 O Syntheses: c total = M, in THF Microwave: 90 min (max. 200W) 30 min cooling Excitation at 366 nm 2 Results MW +H 2 O

2 Results Absorbance and Fluorescence Spectroscopy

2 Results Further analysis: - Dependence on pH - Other ligand systems - Other metal complexes Fluorescence Spectroscopy Cooperation with HZDR

3 Outlook Potentiometry pH Metal complexes Further Fluorescence studies Cooperation with HZDR Liquid-liquid extraction Current work: Cu(II)/Eu(III) Planned works: Nd/Tb/Yb(III) U(VI), Cm/Am(III) Supramolecular Gelation Metallogels with Schiff bases and Amides in organic solvents 1 H-NMR-titrations with… Zn 2+, Y 3+, La 3+, UO 2 2+ Further projects

Thank you for your attention.