novel multifunctional n,o,s - donor ligands for d - and f -element complexation
DESCRIPTION
Novel multifunctional N,O,S - donor ligands for d - and f -element complexation. 22.02.2012Juliane März. 1 Introduction. TU Dresden Department of Chemistry and Food Chemistry. 1 Introduction. „Basic research in energy 2020+ and in nuclear safety and disposal “. - PowerPoint PPT PresentationTRANSCRIPT
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
ORR
AminesRNH
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
ON
R
Hydrazones
β-DiketonesCoordination 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
U1N9
O10O16
Schiff Bases
Microwave synthesisof the complex
ON 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 THF1 h heatingctotal = 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 THFMicrowave: 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 SpectroscopyCooperation with HZDR
3 Outlook
PotentiometrypH
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
Amidesin organic solvents
1H-NMR-titrations
with…
Zn2+, Y3+, La3+, UO22+
Furtherprojects
Thank you for your attention.