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Homoleptic tetraazaphenanthrene-based copper(I) complexes: Synthesis, spectroscopic characterization, crystal structures and computational studies.

MPS-Authors
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Kia,  R.
Research Group of Structural Dynamics of (Bio)Chemical Systems, MPI for biophysical chemistry, Max Planck Society;

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Scholz,  M.
Research Group of Structural Dynamics of (Bio)Chemical Systems, MPI for biophysical chemistry, Max Planck Society;

/persons/resource/persons15915

Techert,  S.
Research Group of Structural Dynamics of (Bio)Chemical Systems, MPI for biophysical chemistry, Max Planck Society;

Fulltext (public)

2060818.pdf
(Publisher version), 2MB

Supplementary Material (public)

2060818_Suppl_1.zip
(Supplementary material), 159KB

2060818_Suppl_2.zip
(Supplementary material), 155KB

2060818_Suppl_3.zip
(Supplementary material), 165KB

2060818_Suppl_4.mol2
(Supplementary material), 13KB

2060818_Suppl_5.mol2
(Supplementary material), 14KB

2060818_Suppl_6.mol2
(Supplementary material), 13KB

2060818_Suppl_7.pdf
(Supplementary material), 613KB

Citation

Kia, R., Scholz, M., Raithby, P. R., & Techert, S. (2014). Homoleptic tetraazaphenanthrene-based copper(I) complexes: Synthesis, spectroscopic characterization, crystal structures and computational studies. Inorganica Chimica Acta, 423, 348-357. doi:10.1016/j.ica.2014.08.052.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0023-EE26-5
Abstract
Three new Cu(I) complexes containing bidentate N^N donor ligands with the general formula [Cu(N^N)2][PF6] (N^N = 2,3-diphenyl-6,7-di-p-tolyl-1,4,5,8-tetraazaphenanthrene (L1), 2,3-diphenyl-6,7-di(2-thienyl)-1,4,5,8-tetraazaphenanthrene (L2), and 2,3-diphenyl-6,7-di-p-fluorophenyl-1,4,5,8-tetraazaphenanthrene (L3), were prepared by the reaction of [Cu(CH3CN)4][PF6] with two equivalents of the N^N ligand. Single-crystal X-ray diffraction analysis confirmed that in each complex the metal displays a distorted tetrahedral geometry surrounded by the four N atoms of the two sterically hindered substituted tetraazaphenanthrene (TAP) ligands. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT), calculations were used to study the ground state properties and interpret the absorption spectra for these Cu(I) complexes. The calculations show that the lowest-energy excitations of all complexes are dominated by dπ(Cu) → π∗(L), metal-to-ligand charge transfer, (MLCT) excitations. Electronic difference density maps (EDDMs) were calculated, indicating the change of electron density in the singlet excited states. The degree of filling of the coordination sphere (G parameter) by the ligands was calculated taking into account the ligand–ligand overlap, and compared to the related bis(2,9-disubstituted phenanthroline) Cu(I) complexes.