Structural and magnetic studies on cyano-bridged rectangular Fe 2M2 (M = Cu, Ni) clusters

Wei Liu; Cai Feng Wang; Yi Zhi Li; Jing Lin Zuo; Xiao Zeng You

doi:10.1021/ic061347r

Structural and magnetic studies on cyano-bridged rectangular Fe ₂M₂ (M = Cu, Ni) clusters

Wei Liu, Cai Feng Wang, Yi Zhi Li, Jing Lin Zuo, Xiao Zeng You

Nanjing University

Research output: Contribution to journal › Article › peer-review

97 Scopus citations

Abstract

Using the tricyano precursor, (Bu₄N)[(Tp)Fe(CN)₃] (Tp = Tris(pyrazolyl) hydroborate) (1), four new tetranuclear clusters, [(Tp)Fe(CN)₃Cu(Tp)]₂·2H₂O (2), [(Tp)Fe(CN)₃Cu(bpca)]₂·4H₂O (3) (bpca = bis(2-pyridylcarbonyl)amidate anion), [(Tp)Fe(CN)₃Ni(tren)] ₂(ClO₄)₂·2H₂O (4) (tren = tris(2-amino)ethylamine), and [(Tp)Fe(CN)₃Ni(bipy)₂] ₂[(Tp)-Fe(CN)₃]₂·6H₂O (5) (bipy = 2,2′-bipyridine), have been synthesized and structurally characterized. The four clusters possess similar square structures, where Fe^III and M^II (M = Cu^II or Ni^II) ions alternate at the rectangle corners. There exist intermolecular π-π stacking interactions through pyrazolyl groups of Tp^- ligands in complexes 2 and 4, which lead to 1D chain structures. Complex 5 shows a 3D network structure through the coexistence of π-π stacking effects and hydrogen-bonding interactions. Magnetic studies show intramolecular ferromagnetic interactions in all four clusters. The exchange parameters are +11.91 and +1.38 cm^-1 for clusters 2 and 3, respectively, while uniaxial molecular anisotropy can be detected in complex 3 due to the distorted core in its molecular structure. Complex 4 has a ground state of S = 3 and shows SMM behavior with an effective energy barrier of U = 18.9 cm^-1. Unusual spin-glass-like dynamic relaxations are observed for complex 5.

Original language	English
Pages (from-to)	10058-10065
Number of pages	8
Journal	Inorganic Chemistry
Volume	45
Issue number	25
DOIs	https://doi.org/10.1021/ic061347r
State	Published - 11 Dec 2006
Externally published	Yes

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@article{5bcbf648fcf5419c934204ff578ecb17,

title = "Structural and magnetic studies on cyano-bridged rectangular Fe 2M2 (M = Cu, Ni) clusters",

abstract = "Using the tricyano precursor, (Bu4N)[(Tp)Fe(CN)3] (Tp = Tris(pyrazolyl) hydroborate) (1), four new tetranuclear clusters, [(Tp)Fe(CN)3Cu(Tp)]2·2H2O (2), [(Tp)Fe(CN)3Cu(bpca)]2·4H2O (3) (bpca = bis(2-pyridylcarbonyl)amidate anion), [(Tp)Fe(CN)3Ni(tren)] 2(ClO4)2·2H2O (4) (tren = tris(2-amino)ethylamine), and [(Tp)Fe(CN)3Ni(bipy)2] 2[(Tp)-Fe(CN)3]2·6H2O (5) (bipy = 2,2′-bipyridine), have been synthesized and structurally characterized. The four clusters possess similar square structures, where FeIII and MII (M = CuII or NiII) ions alternate at the rectangle corners. There exist intermolecular π-π stacking interactions through pyrazolyl groups of Tp- ligands in complexes 2 and 4, which lead to 1D chain structures. Complex 5 shows a 3D network structure through the coexistence of π-π stacking effects and hydrogen-bonding interactions. Magnetic studies show intramolecular ferromagnetic interactions in all four clusters. The exchange parameters are +11.91 and +1.38 cm-1 for clusters 2 and 3, respectively, while uniaxial molecular anisotropy can be detected in complex 3 due to the distorted core in its molecular structure. Complex 4 has a ground state of S = 3 and shows SMM behavior with an effective energy barrier of U = 18.9 cm-1. Unusual spin-glass-like dynamic relaxations are observed for complex 5.",

author = "Wei Liu and Wang, {Cai Feng} and Li, {Yi Zhi} and Zuo, {Jing Lin} and You, {Xiao Zeng}",

year = "2006",

month = dec,

day = "11",

doi = "10.1021/ic061347r",

language = "英语",

volume = "45",

pages = "10058--10065",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "25",

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TY - JOUR

T1 - Structural and magnetic studies on cyano-bridged rectangular Fe 2M2 (M = Cu, Ni) clusters

AU - Liu, Wei

AU - Wang, Cai Feng

AU - Li, Yi Zhi

AU - Zuo, Jing Lin

AU - You, Xiao Zeng

PY - 2006/12/11

Y1 - 2006/12/11

N2 - Using the tricyano precursor, (Bu4N)[(Tp)Fe(CN)3] (Tp = Tris(pyrazolyl) hydroborate) (1), four new tetranuclear clusters, [(Tp)Fe(CN)3Cu(Tp)]2·2H2O (2), [(Tp)Fe(CN)3Cu(bpca)]2·4H2O (3) (bpca = bis(2-pyridylcarbonyl)amidate anion), [(Tp)Fe(CN)3Ni(tren)] 2(ClO4)2·2H2O (4) (tren = tris(2-amino)ethylamine), and [(Tp)Fe(CN)3Ni(bipy)2] 2[(Tp)-Fe(CN)3]2·6H2O (5) (bipy = 2,2′-bipyridine), have been synthesized and structurally characterized. The four clusters possess similar square structures, where FeIII and MII (M = CuII or NiII) ions alternate at the rectangle corners. There exist intermolecular π-π stacking interactions through pyrazolyl groups of Tp- ligands in complexes 2 and 4, which lead to 1D chain structures. Complex 5 shows a 3D network structure through the coexistence of π-π stacking effects and hydrogen-bonding interactions. Magnetic studies show intramolecular ferromagnetic interactions in all four clusters. The exchange parameters are +11.91 and +1.38 cm-1 for clusters 2 and 3, respectively, while uniaxial molecular anisotropy can be detected in complex 3 due to the distorted core in its molecular structure. Complex 4 has a ground state of S = 3 and shows SMM behavior with an effective energy barrier of U = 18.9 cm-1. Unusual spin-glass-like dynamic relaxations are observed for complex 5.

AB - Using the tricyano precursor, (Bu4N)[(Tp)Fe(CN)3] (Tp = Tris(pyrazolyl) hydroborate) (1), four new tetranuclear clusters, [(Tp)Fe(CN)3Cu(Tp)]2·2H2O (2), [(Tp)Fe(CN)3Cu(bpca)]2·4H2O (3) (bpca = bis(2-pyridylcarbonyl)amidate anion), [(Tp)Fe(CN)3Ni(tren)] 2(ClO4)2·2H2O (4) (tren = tris(2-amino)ethylamine), and [(Tp)Fe(CN)3Ni(bipy)2] 2[(Tp)-Fe(CN)3]2·6H2O (5) (bipy = 2,2′-bipyridine), have been synthesized and structurally characterized. The four clusters possess similar square structures, where FeIII and MII (M = CuII or NiII) ions alternate at the rectangle corners. There exist intermolecular π-π stacking interactions through pyrazolyl groups of Tp- ligands in complexes 2 and 4, which lead to 1D chain structures. Complex 5 shows a 3D network structure through the coexistence of π-π stacking effects and hydrogen-bonding interactions. Magnetic studies show intramolecular ferromagnetic interactions in all four clusters. The exchange parameters are +11.91 and +1.38 cm-1 for clusters 2 and 3, respectively, while uniaxial molecular anisotropy can be detected in complex 3 due to the distorted core in its molecular structure. Complex 4 has a ground state of S = 3 and shows SMM behavior with an effective energy barrier of U = 18.9 cm-1. Unusual spin-glass-like dynamic relaxations are observed for complex 5.

UR - http://www.scopus.com/inward/record.url?scp=33846125229&partnerID=8YFLogxK

U2 - 10.1021/ic061347r

DO - 10.1021/ic061347r

M3 - 文章

AN - SCOPUS:33846125229

SN - 0020-1669

VL - 45

SP - 10058

EP - 10065

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 25

ER -

Structural and magnetic studies on cyano-bridged rectangular Fe ₂M₂ (M = Cu, Ni) clusters

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