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 | |
| State | Published - Jul 1 2012 |
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Keywords
- Chain compounds
- Magnetic susceptibility
- Pyrophosphate
- X-ray crystal structures
ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry
- Materials Chemistry
Cite this
Synthesis, structural, thermal, and magnetic investigations of Co(II), Ni(II), and Mn(II) pyrophosphate chains. / Hoffman, Amanda E.; Marino, Nadia; Lloret, Francesc; Julve, Miguel; Doyle, Robert Patrick.
In: Inorganica Chimica Acta, Vol. 389, 01.07.2012, p. 151-158.Research output: Contribution to journal › Article
}
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 Patrick
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
UR - http://www.scopus.com/inward/record.url?scp=84861652019&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84861652019&partnerID=8YFLogxK
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 -