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Homo‐ and Heteronuclear Compounds with a Symmetrical Bis‐hydrazone Ligand: Synthesis, Structural Studies, and Luminescent Properties
Author(s) -
RodríguezHermida Sabina,
Lago Ana B.,
Carballo Rosa,
Fabelo Oscar,
VázquezLópez Ezequiel M.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405962
Subject(s) - heteronuclear molecule , chemistry , deprotonation , ligand (biochemistry) , luminescence , hydrazone , metal , crystallography , metal ions in aqueous solution , crystal structure , coordination sphere , derivative (finance) , stereochemistry , medicinal chemistry , nuclear magnetic resonance spectroscopy , ion , organic chemistry , materials science , biochemistry , receptor , optoelectronics , financial economics , economics
Nine new coordination compounds have been synthesized by the reaction of salts of bivalent metal ions (a=Zn II , b=Cu II , c=Ni II , d=Co II ) with the bis(benzoylhydrazone) derivative of 4,6‐diacetylresorcinol (H 4 L). Three kinds of complexes have been obtained: homodinuclear compounds [M 2 (H 2 L) 2 ]⋅ n H 2 O ( 1 a , 1 b , 1 c , and 1 d ), homotetranuclear compounds [M 4 (L) 2 ]⋅ n (solv) ( 2 a and 2 c ), and heterotetranuclear compounds [Zn 2 M 2 (L) 2 ]⋅ n (solv) ( 2 ab , 2 ac , and 2 ad ). The structures of the free ligand H 4 L⋅2 DMSO and its complexes [Zn 2 (H 2 L) 2 (DMSO) 2 ] ( 1 a* ), [Zn 4 (L) 2 (DMSO) 6 ] ( 2 a* ), and [Zn 0.45 Cu 3.55 (L) 2 (DMSO) 6 ]⋅2 DMSO ( 2 ab* ) were elucidated by single‐crystal X‐ray diffraction. The ligand shows luminescence properties and its fluorimetric behavior towards M II metals (M=Zn, Cu, Ni and Co) has been studied. Furthermore, the solid‐state luminescence properties of the ligand and compounds have been determined at room temperature. 1 H NMR spectroscopic monitoring of the reaction of H 4 L with Zn II showed the deprotonation sequence of the OH/NH groups upon metal coordination. Heteronuclear reactions have also been monitored by using ESI‐MS and spectrofluorimetric techniques.