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.
N1 - Funding Information:
R.P.D. wishes to thank the American Chemical Society for a Doctoral New Investigator Award (48999-DNI 3) and the office of the Vice-President for research at Syracuse University for postdoctoral funding for N.M. Thanks are due to the Ministerio Español de Ciencia e Innovación (Project CTQ2010-15364) for financial support.
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 (Na4P 2O7) at low pH (∼2) afforded three isostructural pyrophosphate complexes of an unprecedented one-dimensional typology, namely, {[M(phen)(H2O)(H2P2O7)] ·H2O}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-P2O7)}·6MeOH (1a), {[Ni(phen)2]2(H2O)(μ-P2O 7)}·27H2O (2a) and {[Mn(phen)2] 2(H2O)(μ-P2O7)}·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 (Na4P 2O7) at low pH (∼2) afforded three isostructural pyrophosphate complexes of an unprecedented one-dimensional typology, namely, {[M(phen)(H2O)(H2P2O7)] ·H2O}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-P2O7)}·6MeOH (1a), {[Ni(phen)2]2(H2O)(μ-P2O 7)}·27H2O (2a) and {[Mn(phen)2] 2(H2O)(μ-P2O7)}·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
M3 - Article
AN - SCOPUS:84861652019
VL - 389
SP - 151
EP - 158
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
SN - 0020-1693
ER -