On the electronic structure and spectroscopic properties of a pseudo-tetrahedral cationic cobalt(ii) tetraamine complex-([35]adamanzane)cobalt(ii)

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The electronic structure and spectrum of the unusual pseudo-tetrahedral cobalt(ii) coordination compound formed with the bicyclic tetraamine ligand 1,5,9,13-tetraazabicyclo[7.7.3]nonadecane ([35]adz) has been investigated. The ligand-field absorption spectrum of the quartet ground state of the [Co([35]adz)]2+ cation was resolved into five components, which were assigned by application of angular overlap model (AOM) calculations. Furthermore, density functional theory (DFT) and time-dependent DFT (TD-DFT) were applied to investigate the structure and absorption spectrum of the cation using the B3LYP functional in combination with various basis sets. The DFT calculations provided a geometry for the cation in excellent agreement with the crystal structure of [Co([35]adz)]ZnCl4. The theoretical investigation of the electronic spectrum of the cation shows that TD-DFT can successfully be applied to open shell transition metal compounds, although only spin-allowed, single electron transitions are accounted for.

Original languageEnglish
JournalJournal of the Chemical Society. Dalton Transactions
Volume3
Issue number16
Pages (from-to)3199-3204
Number of pages6
ISSN1477-9226
DOIs
Publication statusPublished - 7 Aug 2003

    Research areas

  • Angular overlap model (AOM), Cobalt, Density functional calculations, Macrocycles, Structural studies

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