Novel multifunctional N,O,S - donor ligands for

d- and f-element complexation

22.02.2012 Juliane März

TU Dresden

Department of

Chemistry and Food

Chemistry

1 Introduction

„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

Members of our groupand their fields of research

Porphyrines

Schiff bases

β-Diketones/Hydrazones

Amides Schiff bases

1 Introduction

Ligand systems

Schiff basesβ-Diketones Diamides

RN

RR

O

R

O

NH

O

NH

O

RR

Amines

RNH

R

Synthesis and characterisation

Characteristics of complexation

- Spectroscopy: ESI-MS, NMR, IR, UV/Vis, Fluorescence

- X-ray analysis

- Potentiometry

- Liquid-liquid extraction

1 Introduction

RNH

O

NR

Hydrazones

β-Diketones

Coordination of Eu(III): [Eu(L)3(H2O)2]·THF

2 Results

NN

O OH

O2 donor set

CN = 8

Complex Synthesis:

- THF

- Deprotonation agent Na2CO3

Hydazones

2 Results

Coordination of UO22+: (Et3NH)2[(UO2)2(μ-O2)(L)2]MeOH

N NHN NH

O ON N

Complex Synthesis:

- MeOH

- Deprotonation agent Et3N

N2O2 donor set

CN = 8

U1

N9

O10O16

Schiff Bases

Microwave synthesis

of the complexO

N N

OH HO

Coordination of UO22+: [UO2(L)]

2 Results

N2O3 donor set

CN = 7

N,N‘,N‘‘-Tris(2-picolyl)methane tricarboxamide

Left-handed triple N‒H…O hydrogen bond helix

Amides

NH

NH

O O

OHNN N

N

2 Results

X-ray analysis

UV/Vis Spectroscopy: Fe(III)

Job Plot at 660 nm:2:1 ratio (L:Fe3+)

Fe(NO3)3·6H2O, ctotal = 2.5·10-4 M in MeOH

NH

NH

O O

OHNN N

N2 Results

UV/Vis Spectroscopy : La(III)

La(NO3)3·6H2O

NH

NH

O O

OHNN N

N

Preparation of the samples:

10-2 M in THF

1 h heating

ctotal = 4·10-3 M in MeOH

2 Results

Gd(III)-complex of L1

Luminescence of Ln(III)- complexes in THF, H2O and EtOH/H2O

NH

NH

O O

OHNN N

N

Syntheses:

ctotal = 10-2 M, in THF

Microwave: 90 min (max. 200W)

30 min cooling

Excitation at 366 nm

2 Results

MW +H2O

NH

NH

O O

OHNN N

N2 Results

Absorbance and Fluorescence Spectroscopy

NH

NH

O O

OHNN N

N2 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

1H-NMR-titrations

with…

Zn2+, Y3+, La3+, UO22+

Further

projects

Thank you for your attention.