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

Peter W. Thulstrup; Louise Broge; Erik Larsen; Johan Springborg

doi:10.1039/b305712g

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

Peter W. Thulstrup, Louise Broge, Erik Larsen, Johan Springborg

Kemisk Institut

Abstract

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.

Originalsprog	Engelsk
Tidsskrift	Journal of the Chemical Society. Dalton Transactions
Vol/bind	3
Udgave nummer	16
Sider (fra-til)	3199-3204
Antal sider	6
ISSN	1477-9226
DOI	https://doi.org/10.1039/b305712g
Status	Udgivet - 7 aug. 2003

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Citationsformater

On the electronic structure and spectroscopic properties of a pseudo-tetrahedral cationic cobalt(ii) tetraamine complex-([3⁵]adamanzane)cobalt(ii). / Thulstrup, Peter W.; Broge, Louise; Larsen, Erik et al.

I: Journal of the Chemical Society. Dalton Transactions, Bind 3, Nr. 16, 07.08.2003, s. 3199-3204.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

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abstract = "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.",

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AU - Larsen, Erik

AU - Springborg, Johan

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N2 - 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.

AB - 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.

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