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Spectroscopic, EPR, X-ray structural, and DFT studies of the complex compound of N4-donor ligand with copper(II)

Spectroscopic, EPR, X-ray structural, and DFT studies of the complex compound of N4-donor ligand with copper(II)
Spectroscopic, EPR, X-ray structural, and DFT studies of the complex compound of N4-donor ligand with copper(II)
A new mononuclear neutral five-coordinate copper(II) coordination compound [Cu(L)(H2O)] (1) (L = 6,6′-bis(NH-benzimidazol-2-yl)-2,2′-bipyridine) was synthesized and characterized by IR, UV–Vis, EPR and LC-MS (APCI) analysis. The crystal structure was also determined by X-ray crystallography. In 1, the copper(II) center adopts a five-coordinate distorted square-pyramidal (SP) geometry in which the basal plane formed by four of the nitrogen atoms of the ligand while the apical position is occupied by the oxygen atom of the water molecule. The four Cu–N bond lengths are 1.987(4), 1.992(4), 2.020(5) and 2.027(4) Å, and the longest bond of the apical Cu−Ow is 2.234(4) Å. The ligand undergoes deprotonation upon coordination to the metal center and acts as a dianionic tetradentate chelate to form a neutral complex [CuN4O]. The X-band EPR data of 1 are in agreement with the crystallographic data indicating a typical five-coordinate SP geometry. This geometry is also obtained by Density Functional Theory calculations. Time-dependent (TD) DFT calculations were used to shed light on the assignment and the nature of the electronic transitions observed in the UV–Vis spectrum. The calculated results are found to be consistent with the experimental data. Non-linear optical properties were also calculated by DFT calculations.
copper, EPR, Tetradentate, Bipyridine, benzimidazole, density functional theory
0022-2860
Yilmaz, Ismail
e3ef6762-1240-4013-b3d1-b7ea926136ae
Acar, Nursel S.
66ee95e0-87b7-4c6f-aa51-2575bed3d818
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Şengül, Abdurrahman
eff3416d-04cc-4bf9-a787-06b11163c3dd
Yilmaz, Ismail
e3ef6762-1240-4013-b3d1-b7ea926136ae
Acar, Nursel S.
66ee95e0-87b7-4c6f-aa51-2575bed3d818
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Şengül, Abdurrahman
eff3416d-04cc-4bf9-a787-06b11163c3dd

Yilmaz, Ismail, Acar, Nursel S., Coles, Simon J. and Şengül, Abdurrahman (2020) Spectroscopic, EPR, X-ray structural, and DFT studies of the complex compound of N4-donor ligand with copper(II). Journal of Molecular Structure, 1214, [128204]. (doi:10.1016/j.molstruc.2020.128204).

Record type: Article

Abstract

A new mononuclear neutral five-coordinate copper(II) coordination compound [Cu(L)(H2O)] (1) (L = 6,6′-bis(NH-benzimidazol-2-yl)-2,2′-bipyridine) was synthesized and characterized by IR, UV–Vis, EPR and LC-MS (APCI) analysis. The crystal structure was also determined by X-ray crystallography. In 1, the copper(II) center adopts a five-coordinate distorted square-pyramidal (SP) geometry in which the basal plane formed by four of the nitrogen atoms of the ligand while the apical position is occupied by the oxygen atom of the water molecule. The four Cu–N bond lengths are 1.987(4), 1.992(4), 2.020(5) and 2.027(4) Å, and the longest bond of the apical Cu−Ow is 2.234(4) Å. The ligand undergoes deprotonation upon coordination to the metal center and acts as a dianionic tetradentate chelate to form a neutral complex [CuN4O]. The X-band EPR data of 1 are in agreement with the crystallographic data indicating a typical five-coordinate SP geometry. This geometry is also obtained by Density Functional Theory calculations. Time-dependent (TD) DFT calculations were used to shed light on the assignment and the nature of the electronic transitions observed in the UV–Vis spectrum. The calculated results are found to be consistent with the experimental data. Non-linear optical properties were also calculated by DFT calculations.

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Accepted/In Press date: 2 April 2020
e-pub ahead of print date: 11 April 2020
Keywords: copper, EPR, Tetradentate, Bipyridine, benzimidazole, density functional theory

Identifiers

Local EPrints ID: 439719
URI: http://eprints.soton.ac.uk/id/eprint/439719
ISSN: 0022-2860
PURE UUID: 246e82e9-73d0-434e-89d8-2f4737138a05
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 30 Apr 2020 16:31
Last modified: 22 May 2020 00:26

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