Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
10558324 | Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy | 2005 | 12 Pages |
Abstract
The use of di-2-pyridyl ketone, (py)2CO, in zinc(II) nitrate chemistry has yielded a dinuclear complex and a cationic tetranuclear cluster. The 1:1 Zn(NO3)2·4H2O/(py)2CO reaction system in EtOH gives [Zn2(NO3)2{(py)2C(OEt)O}2]·0.5H2O (1·0.5H2O), whereas the same reaction system in MeCN yields [Zn4(NO3)3{(py)2C(OH)O}4(H2O)](NO3) (2). The monoanionic derivatives of the hemiacetal and the gem-diol forms of di-2-pyridyl ketone have been derived from the Zn(II)-mediated addition of solvent (EtOH, H2O involved in MeCN) on the carbonyl group of (py)2CO. Each (py)2C(OEt)Oâ ion functions as an η1:η2:η1:μ2 ligand in 1·0.5H2O chelating the two ZnII atoms through the 2-pyridyl nitrogen atoms and the common bridging, deprotonated oxygen atom; one asymmetric chelating nitrate completes six coordination at each metal center. The tetranuclear cluster cation of 2 has a cubane topology with the ZnII ions and the deprotonated oxygen atoms from the four η1:η3:η1:μ3 (py)2C(OH)Oâ ligands occupying alternate vertices. Three monodentate nitrates and one aqua ligand complete the sixth coordination site at the metal ions. The two complexes have been characterized by IR and far-IR spectroscopies. Characteristic bands are discussed in terms of the known structures and the coordination modes of the nitrato ligands. Upon excitation at 371 nm, complex 2 displays blue photoluminescence in the solid state at room temperature with two emission maxima at 430 and 455 nm.
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Physical Sciences and Engineering
Chemistry
Analytical Chemistry
Authors
Eugenia Katsoulakou, Vlasoula Bekiari, Catherine P. Raptopoulou, Aris Terzis, Panagiotis Lianos, Evy Manessi-Zoupa, Spyros P. Perlepes,