Synthesis, structural, thermal, and magnetic investigations of Co(II), Ni(II), and Mn(II) pyrophosphate chains

Amanda E. Hoffman; Nadia Marino; Francesc Lloret; Miguel Julve; Robert P. Doyle

doi:10.1016/j.ica.2012.01.054

Synthesis, structural, thermal, and magnetic investigations of Co(II), Ni(II), and Mn(II) pyrophosphate chains

Amanda E. Hoffman, Nadia Marino, Francesc Lloret, Miguel Julve, Robert P. Doyle

Research output: Contribution to journal › Article

8 Scopus citations

Abstract

The reaction in water of cobalt(II), nickel(II) or manganese(II) chloride with 1,10-phenanthroline (phen) and sodium pyrophosphate (Na ₄P ₂O ₇) at low pH (∼2) afforded three isostructural pyrophosphate complexes of an unprecedented one-dimensional typology, namely, {[M(phen)(H ₂O)(H ₂P ₂O ₇)] ·H ₂O} _n with M = Co(1), Ni(2) and Mn(3). The di-hydrogen-pyrophosphate anion featured in these complexes adopts a rare bidentate/monodentate bridging mode leading to chain propagation. This unusual bridging pathway produces a metal-metal intra-chain separation of about 6.6-6.7 Å for 1-3, values much larger than the metal-metal distance across the classic bis-bidentate PPi in the parent homodinuclear complexes {[Co(phen) ₂] ₂(μ-P ₂O ₇)}·6MeOH (1a), {[Ni(phen) ₂] ₂(H ₂O)(μ-P ₂O ₇)}·27H ₂O (2a) and {[Mn(phen) ₂] ₂(H ₂O)(μ-P ₂O ₇)}·13H ₂O (3a), corresponding to ca. 4.9, 5.0 and 4.7 Å, respectively. Variable-temperature magnetic susceptibility measurements on polycrystalline samples of 1-3 revealed weak intrachain antiferromagnetic couplings [J = -0.93 (1), -1.88 (2) and -0.26 cm ^-1 (3)], consistent with previous data on the dinuclear complexes 1a-3a.

Original language	English (US)
Pages (from-to)	151-158
Number of pages	8
Journal	Inorganica Chimica Acta
Volume	389
DOIs	https://doi.org/10.1016/j.ica.2012.01.054
State	Published - Jul 1 2012

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Keywords

Chain compounds
Magnetic susceptibility
Pyrophosphate
X-ray crystal structures

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Cite this

Hoffman, A. E., Marino, N., Lloret, F., Julve, M., & Doyle, R. P. (2012). Synthesis, structural, thermal, and magnetic investigations of Co(II), Ni(II), and Mn(II) pyrophosphate chains. Inorganica Chimica Acta, 389, 151-158. https://doi.org/10.1016/j.ica.2012.01.054

@article{67b59e6e82d04c4781b9143126ed5d2e,

title = "Synthesis, structural, thermal, and magnetic investigations of Co(II), Ni(II), and Mn(II) pyrophosphate chains",

abstract = "The reaction in water of cobalt(II), nickel(II) or manganese(II) chloride with 1,10-phenanthroline (phen) and sodium pyrophosphate (Na 4P 2O 7) at low pH (∼2) afforded three isostructural pyrophosphate complexes of an unprecedented one-dimensional typology, namely, {[M(phen)(H 2O)(H 2P 2O 7)] ·H 2O} n with M = Co(1), Ni(2) and Mn(3). The di-hydrogen-pyrophosphate anion featured in these complexes adopts a rare bidentate/monodentate bridging mode leading to chain propagation. This unusual bridging pathway produces a metal-metal intra-chain separation of about 6.6-6.7 {\AA} for 1-3, values much larger than the metal-metal distance across the classic bis-bidentate PPi in the parent homodinuclear complexes {[Co(phen) 2] 2(μ-P 2O 7)}·6MeOH (1a), {[Ni(phen) 2] 2(H 2O)(μ-P 2O 7)}·27H 2O (2a) and {[Mn(phen) 2] 2(H 2O)(μ-P 2O 7)}·13H 2O (3a), corresponding to ca. 4.9, 5.0 and 4.7 {\AA}, respectively. Variable-temperature magnetic susceptibility measurements on polycrystalline samples of 1-3 revealed weak intrachain antiferromagnetic couplings [J = -0.93 (1), -1.88 (2) and -0.26 cm -1 (3)], consistent with previous data on the dinuclear complexes 1a-3a.",

keywords = "Chain compounds, Magnetic susceptibility, Pyrophosphate, X-ray crystal structures",

author = "Hoffman, {Amanda E.} and Nadia Marino and Francesc Lloret and Miguel Julve and Doyle, {Robert P.}",

year = "2012",

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doi = "10.1016/j.ica.2012.01.054",

language = "English (US)",

volume = "389",

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TY - JOUR

T1 - Synthesis, structural, thermal, and magnetic investigations of Co(II), Ni(II), and Mn(II) pyrophosphate chains

AU - Hoffman, Amanda E.

AU - Marino, Nadia

AU - Lloret, Francesc

AU - Julve, Miguel

AU - Doyle, Robert P.

PY - 2012/7/1

Y1 - 2012/7/1

N2 - The reaction in water of cobalt(II), nickel(II) or manganese(II) chloride with 1,10-phenanthroline (phen) and sodium pyrophosphate (Na 4P 2O 7) at low pH (∼2) afforded three isostructural pyrophosphate complexes of an unprecedented one-dimensional typology, namely, {[M(phen)(H 2O)(H 2P 2O 7)] ·H 2O} n with M = Co(1), Ni(2) and Mn(3). The di-hydrogen-pyrophosphate anion featured in these complexes adopts a rare bidentate/monodentate bridging mode leading to chain propagation. This unusual bridging pathway produces a metal-metal intra-chain separation of about 6.6-6.7 Å for 1-3, values much larger than the metal-metal distance across the classic bis-bidentate PPi in the parent homodinuclear complexes {[Co(phen) 2] 2(μ-P 2O 7)}·6MeOH (1a), {[Ni(phen) 2] 2(H 2O)(μ-P 2O 7)}·27H 2O (2a) and {[Mn(phen) 2] 2(H 2O)(μ-P 2O 7)}·13H 2O (3a), corresponding to ca. 4.9, 5.0 and 4.7 Å, respectively. Variable-temperature magnetic susceptibility measurements on polycrystalline samples of 1-3 revealed weak intrachain antiferromagnetic couplings [J = -0.93 (1), -1.88 (2) and -0.26 cm -1 (3)], consistent with previous data on the dinuclear complexes 1a-3a.

AB - The reaction in water of cobalt(II), nickel(II) or manganese(II) chloride with 1,10-phenanthroline (phen) and sodium pyrophosphate (Na 4P 2O 7) at low pH (∼2) afforded three isostructural pyrophosphate complexes of an unprecedented one-dimensional typology, namely, {[M(phen)(H 2O)(H 2P 2O 7)] ·H 2O} n with M = Co(1), Ni(2) and Mn(3). The di-hydrogen-pyrophosphate anion featured in these complexes adopts a rare bidentate/monodentate bridging mode leading to chain propagation. This unusual bridging pathway produces a metal-metal intra-chain separation of about 6.6-6.7 Å for 1-3, values much larger than the metal-metal distance across the classic bis-bidentate PPi in the parent homodinuclear complexes {[Co(phen) 2] 2(μ-P 2O 7)}·6MeOH (1a), {[Ni(phen) 2] 2(H 2O)(μ-P 2O 7)}·27H 2O (2a) and {[Mn(phen) 2] 2(H 2O)(μ-P 2O 7)}·13H 2O (3a), corresponding to ca. 4.9, 5.0 and 4.7 Å, respectively. Variable-temperature magnetic susceptibility measurements on polycrystalline samples of 1-3 revealed weak intrachain antiferromagnetic couplings [J = -0.93 (1), -1.88 (2) and -0.26 cm -1 (3)], consistent with previous data on the dinuclear complexes 1a-3a.

KW - Chain compounds

KW - Magnetic susceptibility

KW - Pyrophosphate

KW - X-ray crystal structures

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U2 - 10.1016/j.ica.2012.01.054

DO - 10.1016/j.ica.2012.01.054

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AN - SCOPUS:84861652019

VL - 389

SP - 151

EP - 158

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

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10.1016/j.ica.2012.01.054