Synthesis, characterization, electrochemical studies and X-ray structures of mixed-ligand polypyridyl copper(II) complexes with the acetate

Authors

  • Oluwafunmilayo Adekunle Department of Pure and Applied Chemistry, Ladoke Akintola University of Technology, P.M.B.4000, Ogbomoso
  • Ray Butcher Department of Chemistry, Howard University, Washington DC
  • Oladapo Bakare Department of Chemistry, Howard University, Washington DC
  • Olusegun Odunola Department of Chemistry, Hallmark University, Ijebu Itele, Nigeria

DOI:

https://doi.org/10.2298/JSC160407072A

Keywords:

X-ray structure determination, copper polypyridyl complexes, π–π interactions, CuN4O chromophore, quasi-reversible

Abstract

[Cu(phen)2(CH3COO)](ClO4)·2H2O (1) and

[Cu(bipy)2(CH3COO)](ClO4)·H2O (2) (phen = 1,10-phenanthroline, bipy =
= 2,2′-bipyridine) were synthesized and characterized. The complexes were characterized by employing elemental analyses, infrared and UV–Vis spec­troscopy, room tempe­rature magnetic measurements and the crystal structures were elucidated using X-ray diffraction experiments. The redox properties of the complexes were also investigated. Both structures have a square pyramidal CuN4O chromophore, which exhibit significant distortions due to long Cu–O (2.217(3) Å for 1 and 2.179(1) Å for 2) and Cu–N (2.631(2) Å for 1 and 2.714(1) Å for 2) bonds. This distortion was further shown by the O–Cu–N bond angles (147.71(8)° for 1 and 153.40(5)° for 2). Elemental analyses further supported the structural details unveiled by the single crystal X-ray diffraction analysis. The infrared spectra show the acetate vibrational frequencies at 1587, 1428 and 1314 cm-1 for 1, 1571, 1441 and 1319 cm-1 for 2, and the perchlorate bands at 1059 and 720 cm-1 for 1 and 1080 and 768 cm-1 for 2. The broad d–d bands for the copper ion at 14.514 cm-1 for 1 and 14535 cm-1 for 2 support the adoption of square pyramid geometries. The magnetic moments for the two complexes were 1.83 mB for 1 and 1.72 mB for 2. The peak-to-peak values of the two complexes show that the electrode reactions are quasi-reversible with ΔEp of 0.023 V for 1 and 0.025 V for 2. In both structures, there are π–π intermolecular interactions in addition to hydrogen bonding between the units.

Author Biographies

Oluwafunmilayo Adekunle, Department of Pure and Applied Chemistry, Ladoke Akintola University of Technology, P.M.B.4000, Ogbomoso

Pure and Applied Chemistry, Associate Professor

Ray Butcher, Department of Chemistry, Howard University, Washington DC

Chemistry and Professor

Oladapo Bakare, Department of Chemistry, Howard University, Washington DC

Chemistry and Professor

Olusegun Odunola, Department of Chemistry, Hallmark University, Ijebu Itele, Nigeria

Chemistry and Professor

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Published

2016-11-26

How to Cite

[1]
O. Adekunle, R. Butcher, O. Bakare, and O. Odunola, “Synthesis, characterization, electrochemical studies and X-ray structures of mixed-ligand polypyridyl copper(II) complexes with the acetate”, J. Serb. Chem. Soc., vol. 81, no. 11, pp. 1251-1262, Nov. 2016.

Issue

Section

Inorganic Chemistry