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Synthesis, X-ray Crystallographic, Electrochemical, and Spectroscopic Studies of Bis-(1,10-phenanthroline)(2,2′-bipyridine)cobalt(III) Hexafluorophosphate

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Abstract

The synthesis, X-ray crystallographic, electrochemical, and spectroscopic studies of bis-(1,10-phenanthroline)(2,2′-bipyridine)cobalt(III) hexafluorophosphate with acetone solvent of crystallization ([Co(phen)2(bpy)](PF6)3·1.6(CH3)2CO) is reported. The compound crystallized in a monoclinic space group P2(1)/n with a = 13.215(3) Å, b = 17.823(4) Å, c = 19.823(4) Å, β = 96.80(3)° and V = 4636.1(16) Å3 with Z = 4. The cobalt(III) metal center has a slightly distorted octahedral geometry. 1,10-Phenanthroline and 2,2′-bipyridine ligands were generally planar, and did not exhibit π–π overlap. The packing of the cations was stabilized by hydrogen bonding with hexafluorophosphate anions. The electrochemical studies revealed the CoIII/II, CoII/I and CoI/0 redox couples at E 1/2 = +0.32, −0.91 and −1.61 V (vs AgCl/Ag) respectively in acetonitrile. 59Co NMR spectroscopic studies revealed that the [Co(phen)2(bpy)](PF6)3·0.5(C2H5)2O species has a chemical shift of 6900 ppm in DMSO-d 6.

Graphical Abstract

The mononuclear complex, [Co(phen)2(bpy)](PF6)3·1.6(CH3)2CO) was synthesized and characterized, but more revealing 59Co NMR spectroscopic studies on the complex revealed interesting species in DMSO-d 6.

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Notes

  1. The ratio of ipa/ipc decreased as the scan rate was increases on the glassy carbon working electrode, see supporting information.

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Acknowledgments

AAH would like to thank the National Science Foundation (NSF) for an NSF CAREER Award as this material is based upon work supported by the NSF under CHE-1431172 (formerly CHE – 1151832). AAH would also like to thank Old Dominion University for the start-up package that allowed for the successful completion of this work. The authors would also like to thank Drs. James Hall (Department of Chemistry and Biochemistry, Old Dominion University) and William L. Jarrett (School of Polymers and High-Performance Materials, The University of Southern Mississippi) for their assistance with acquisitions of the 59Co NMR spectra.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, 23529, USA

    Mark A. W. Lawrence, Raj K. Gurung, Michael J. Celestine & Alvin A. Holder

  2. Department of Chemistry, Clemson University, Clemson, SC, 29634-0973, USA

    Colin D. McMillen

  3. QSpex Technologies, Inc., 1525 Bluegrass Lakes Pkwy, Alpharetta, GA, 30004, USA

    Jessa F. Arca

  4. The University of Southern Mississippi, Hattiesburg, MS, 39406-0001, USA

    Jessa F. Arca

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  1. Mark A. W. Lawrence
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Lawrence, M.A.W., McMillen, C.D., Gurung, R.K. et al. Synthesis, X-ray Crystallographic, Electrochemical, and Spectroscopic Studies of Bis-(1,10-phenanthroline)(2,2′-bipyridine)cobalt(III) Hexafluorophosphate. J Chem Crystallogr 45, 427–433 (2015). https://doi.org/10.1007/s10870-015-0610-2

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