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

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

Research output: Contribution to journalArticle

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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). (Figure Presented).

Original languageEnglish (US)
Pages (from-to)6537-6546
Number of pages10
JournalInorganic Chemistry
Volume54
Issue number13
DOIs
StatePublished - Jul 6 2015

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Cobalt
Nickel
cobalt
Metals
nickel
metals
Metal ions
metal ions
Hamiltonians
Chelation
Hydrates
Magnetic susceptibility
hydrates
Chlorides
chlorides
sodium
Single crystals
aqueous solutions
magnetic permeability
X ray diffraction

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Ferromagnetic Coupling in "Double-Bridged" Dihydrogenpyrophosphate Complexes of Cobalt(II) and Nickel(II). / Greenfield, Tiffany J.; Hoffman, Amanda E.; Marino, Nadia; Goos, Alan G.; Lloret, Francesc; Julve, Miguel; Doyle, Robert Patrick.

In: Inorganic Chemistry, Vol. 54, No. 13, 06.07.2015, p. 6537-6546.

Research output: Contribution to journalArticle

Greenfield, Tiffany J. ; Hoffman, Amanda E. ; Marino, Nadia ; Goos, Alan G. ; Lloret, Francesc ; Julve, Miguel ; Doyle, Robert Patrick. / Ferromagnetic Coupling in "Double-Bridged" Dihydrogenpyrophosphate Complexes of Cobalt(II) and Nickel(II). In: Inorganic Chemistry. 2015 ; Vol. 54, No. 13. pp. 6537-6546.
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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) {\AA} (1), 5.3065(8) {\AA} (2), and 5.371(1) {\AA} (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). (Figure Presented).",
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T1 - Ferromagnetic Coupling in "Double-Bridged" Dihydrogenpyrophosphate Complexes of Cobalt(II) and Nickel(II)

AU - Greenfield, Tiffany J.

AU - Hoffman, Amanda E.

AU - Marino, Nadia

AU - Goos, Alan G.

AU - Lloret, Francesc

AU - Julve, Miguel

AU - Doyle, Robert Patrick

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N2 - 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). (Figure Presented).

AB - 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). (Figure Presented).

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