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

TY - JOUR

T1 - On the electronic structure and spectroscopic properties of a pseudo-tetrahedral cationic cobalt(ii) tetraamine complex-([35]adamanzane)cobalt(ii)

AU - Thulstrup, Peter W.

AU - Broge, Louise

AU - Larsen, Erik

AU - Springborg, Johan

PY - 2003/8/7

Y1 - 2003/8/7

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.

KW - Angular overlap model (AOM)

KW - Cobalt

KW - Density functional calculations

KW - Macrocycles

KW - Structural studies

UR - http://www.scopus.com/inward/record.url?scp=85034320046&partnerID=8YFLogxK

U2 - 10.1039/b305712g

DO - 10.1039/b305712g

M3 - Journal article

AN - SCOPUS:85034320046

SN - 1472-7773

VL - 3

SP - 3199

EP - 3204

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 16

ER -