Synthesis and characterization of cobalt(III) tetraaza macrocyclic complexes containing chloro and azido ligands |
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Authors: | Ki-Young Choi Hee-Kune Lee Ki-Jung Kim Haiil Ryu Kyu-Chul Lee Jaejung Ko Moon-Jip Kim |
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Institution: | (1) Department of Chemistry Education, Kongju National University, Kongju, 314-701, Korea;(2) Department of Materials Chemistry, Korea University, Chochiwon, 339-700, Korea;(3) Department of Physics, Soonchunhyang University, Asan, 336-600, Korea |
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Abstract: | The complexes Co(L)Cl2]Cl · 4H2O (1) and Co(L)(N3)2]N3 · 2H2O (2) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo 14,4,01.18,07.12]docosane) have been synthesized, and structurally characterized by X-ray crystallography, spectroscopy and cyclic voltammetry.
The crystal structure of (1) is centrosymmetric and the cobalt(III) atom has an axially elongated octahedral geometry with four nitrogen atoms of the
macrocycle and two chloride ligands. The cobalt(III) ion in (2) is coordinated to four nitrogen atoms from the macrocycle, and two azide ligands in an octahedral environment, which forms
the 1D polymer through hydrogen bonding contacts involving the cation, azide anion and solvent water molecules. Electronic
spectra of the complexes also exhibit a low-spin octahedral environment. Cyclic voltammetry of the complexes undergoes a one-electron
wave corresponding to Co(III)/Co(II) processes. The electronic spectra and electrochemical behaviors of the complexes are
significantly affected by the nature of the axial ligands. |
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