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Self-Assembly, Structure and Solution Dynamics of Tetranuclear ZnII Hydrazone [2x2] Grid - Type
European Journal of Inorganic Chemistry (2006)
  • Mihail Barboiu
  • Mario Ruben
  • Georges Blasen
  • Nathalie Kyritsakas
  • Elizabeth Chacko, University of Detroit Mercy
  • Manisha Dutta, University of Detroit Mercy
  • Olga Radekovich, University of Detroit Mercy
  • Kimberly Lenton, University of Detroit Mercy
  • David J R Brook, San Jose State University
  • Jean-Marie Lehn
e describe the self-assembly processes as well as the structural and physico-chemical properties of [2×2]Zn2+4 grid complexes involving the bis-tridentate ligands 7–12, based on bis(hydrazone)pyrimidine complexation subunits and octahedrally coordinated Zn2+ ions. The NMR spectroscopic data and the X-ray crystal structure results indicate that in solution and in the solid state the complexes 13–18 adopt a very compact arrangement providing stable [2×2] hydrazone-grid arrays. The π–π stacking between the phenyl ring and the hydrazone units of the perpendicular ligands in the complexes induces a perfect orthogonal arrangement suitable for applications in self-organized metallosupramolecular systems. Zinc complexes provide an opportunity to study the acid–base chemistry without the added effects due to paramagnetism or redox chemistry. The intermediate protonated grids undergo relatively rapid proton exchange on the NMR timescale, the presence of a sharp pyrimidine proton resonance suggesting that there is significant delocalization of the negative charge along the backbone of the ligand. Rotation of the phenyl ring is observed. It involves probably a mechanism in which one of the ligands partially dissociates allowing the initially intercalated phenyl group to rotate, before recoordination of the terminal pyridine.
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Mihail Barboiu, Mario Ruben, Georges Blasen, Nathalie Kyritsakas, et al.. "Self-Assembly, Structure and Solution Dynamics of Tetranuclear ZnII Hydrazone [2x2] Grid - Type" European Journal of Inorganic Chemistry Vol. 2006 Iss. 4 (2006)
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