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Greenfield TJ, Hoffman AE, Marino N, et al. Ferromagnetic Coupling in "Double-Bridged" Dihydrogenpyrophosphate Complexes of Cobalt(II) and Nickel(II). Inorg Chem. 2015;54(13):6537-46doi: 10.1021/acs.inorgchem.5b00866.
Greenfield, T. J., Hoffman, A. E., Marino, N., Goos, A. G., Lloret, F., Julve, M., & Doyle, R. P. (2015). Ferromagnetic Coupling in "Double-Bridged" Dihydrogenpyrophosphate Complexes of Cobalt(II) and Nickel(II). Inorganic chemistry, 54(13), 6537-46. https://doi.org/10.1021/acs.inorgchem.5b00866
Greenfield, Tiffany J, et al. "Ferromagnetic Coupling in "Double-Bridged" Dihydrogenpyrophosphate Complexes of Cobalt(II) and Nickel(II)." Inorganic chemistry vol. 54,13 (2015): 6537-46. doi: https://doi.org/10.1021/acs.inorgchem.5b00866
Greenfield TJ, Hoffman AE, Marino N, Goos AG, Lloret F, Julve M, Doyle RP. Ferromagnetic Coupling in "Double-Bridged" Dihydrogenpyrophosphate Complexes of Cobalt(II) and Nickel(II). Inorg Chem. 2015 Jul 06;54(13):6537-46. doi: 10.1021/acs.inorgchem.5b00866. Epub 2015 Jun 23. PMID: 26103521.
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Inorg Chem. 2015 Jul 06;54(13):6537-46. doi: 10.1021/acs.inorgchem.5b00866. Epub 2015 Jun 23.

Ferromagnetic Coupling in "Double-Bridged" Dihydrogenpyrophosphate Complexes of Cobalt(II) and Nickel(II).

Inorganic chemistry

Tiffany J Greenfield, Amanda E Hoffman, Nadia Marino, Alan G Goos, Francesc Lloret, Miguel Julve, Robert P Doyle

Affiliations

  1. †Department of Chemistry, Syracuse University, Syracuse, New York 13244-4100, United States.
  2. ‡Departament de Quimica Inorganica/Instituto de Ciencia Molecular, Facultat de Química, Universitat de València, Catedratico Jose Beltran 2, 46980 Paterna, Valencia, Spain.

PMID: 26103521 DOI: 10.1021/acs.inorgchem.5b00866

Abstract

Three isostructural compounds of the formula {[M(bipy)(H2O)(H2P2O7)]2·2H2O} [bipy = 2,2'-bipyridine; M = Ni (1), Co (2), Mn (3)] have been isolated from aqueous solutions containing the corresponding metal(II) chloride hydrate with a bipy and sodium pyrophosphate solution in a 1:1:2 molar ratio, and their structures were determined by single-crystal X-ray diffraction. The structures of 1-3 consist of neutral aqua(2,2'-bipyridine)metal(II) dinuclear units bridged by two dihydrogenpyrophosphate groups adopting a bidentate/monodentate mode. Each metal ion in 1-3 is six-coordinate in a distorted octahedral geometry, with the reduced value of the angle subtended by the chelating bipy at the metal ion [79.6(1)° (1), 77.32(7)° (2), and 72.9(1)° (3)] being the main source of this distortion. The values of the intramolecular metal-metal separation are 5.271(1) Å (1), 5.3065(8) Å (2), and 5.371(1) Å (3). Magnetic susceptibility measurements on polycrystalline samples of 1-3 in the temperature range 1.9-300 K shows weak intramolecular ferromagnetic [J = +1.86(2) cm(-1) (1) and +0.25(1) cm(-1) (2)] and antiferromagnetic [J = -0.48(1) cm(-1) (3)] coupling, with the spin Hamiltonian being defined as H = -JSM1·SM1a. This rarely observed coordination mode for dihydrogenpyrophosphate leads to ferromagnetic coupling in complexes of nickel(II) or cobalt(II).

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