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Title: Structure, reactivity, luminescence and magnetism of dinuclear Ln 3+ complexes produced by the Ln3+-assisted hydrolysis of 3,6-bis(2-pyridyl)tetrazine
Authors: Panayiotidou, Lefkia 
Drouza, Chryssoula 
Arabatzis, Nikos B. 
Lianos, Panagiotis 
Stathatos, Elias 
Viskadourakis, Zacharias 
Giapintzakis, John 
Keramidas, Anastasios D. 
Major Field of Science: Agricultural Sciences
Field Category: Agricultural Biotechnology
Keywords: Praseodymium;Samarium;Europium;Gadolinium;Terbium;Dysprosium;Acylhydrazone;Crystal structure;Reactivity;Luminescence;Magnetism
Issue Date: 12-Nov-2013
Source: Polyhedron, 2013, vol. 64, pp. 308-320
Volume: 64
Start page: 308
End page: 320
Journal: Polyhedron 
Abstract: Twelve Pr3+, Sm3+, Eu3+, Gd3+, Tb3+ and Dy3+ complexes of N-(pyridin-2-ylmethylene) picolinohydrazonate (phzp-) were synthesized by the Ln3+ assisted hydrolysis of 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine. Crystallographic characterization of Pr3+, Sm3+ and Eu3+ hydrazonate complexes with nitrate or trifluoroacetyleacetonate co-ligands shows them to have binuclear structures with a planar Ln2O2 core and the ligand to be in its mono-anionic form. Exception is the Pr 3+ complex with nitrate co-ligand, which is a mononuclear species containing the neutral hydrazone. Paramagnetic 1D 1H and 2D gCOSY and gNOESY-gEXSY 1H NMR spectroscopies revealed the presence of different isomers exhibiting a sterically controlled fluxional behavior. In addition, phzp- significantly enhances the luminescence of Eu 3+ and Tb3+. Magnetic measurements show antiferromagnetic coupling between the Ln3+ ions in the dinuclear complexes. The structural characterization of the complexes in both solid state and solution show the versatility of phzp- ligand to adopt various ligating motifs.
ISSN: 0277-5387
DOI: 10.1016/j.poly.2013.05.037
Rights: © Elsevier
Type: Article
Affiliation : Cyprus University of Technology 
University of Cyprus 
University of Patras 
Technological Education Institute of Patras 
Foundation of Research and Technology (F.O.R.T.H.) 
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