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

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Presentation on theme: "Novel multifunctional N,O,S - donor ligands for d- and f-element complexation 22.02.2012Juliane März."— Presentation transcript:

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

2 TU Dresden Department of Chemistry and Food Chemistry 1 Introduction

3 Basic research in energy 2020+ 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

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

5 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

6 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

7 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

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

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

10 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

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

12 Gd(III)-complex of L1 Luminescence of Ln(III)- complexes in THF, H 2 O and EtOH/H 2 O Syntheses: c total = 10 -2 M, in THF Microwave: 90 min (max. 200W) 30 min cooling Excitation at 366 nm 2 Results MW +H 2 O

13 2 Results Absorbance and Fluorescence Spectroscopy

14 2 Results Further analysis: - Dependence on pH - Other ligand systems - Other metal complexes Fluorescence Spectroscopy Cooperation with HZDR

15 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

16 Thank you for your attention.


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