Syntheses, structures, and magnetic properties of cyano-bridged heterobimetallic complexes based on [Fe(bpca)(CN)3]-

He Rui Wen; Cai Feng Wang; Jing Lin Zuo; You Song; Xi Rui Zeng; Xiao Zeng You

doi:10.1021/ic0511468

Syntheses, structures, and magnetic properties of cyano-bridged heterobimetallic complexes based on [Fe(bpca)(CN)₃]^-

He Rui Wen, Cai Feng Wang, Jing Lin Zuo, You Song, Xi Rui Zeng, Xiao Zeng You

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Abstract

Two new cyano-bridged one-dimensional heterobimetallic coordination polymers, [(bpca)₂Fe^III₂(CN) ₆Cu(H₂O)₂·1.5H₂O] _n (2) and [(bpca)Fe^III(CN)₃Cu(bpca)(H ₂O)·H₂O]_n (3), and a trinuclear complex, [(bpca)₂Fe^III₂(CN)₆Mn(CH ₃OH)₂(H₂O)₂]·2H₂O (4), have been synthesized using the tailored tricyanometalate precursor (Bu₄N)[Fe(bpca)(CN)₃]·H₂O (1) (Bu ₄N⁺ = tetrabutylammonium cation; bpca = bis(2-pyridylcarbonyl)amidate anion) as a building block and structurally characterized. In complex 2, the Cu^II ions are six-coordinated in an elongated distorted octahedral environment, and they are linked by distorted octahedrons of [Fe(bpca)(CN)₃]^- to form 1D chain of squares. Complex 3 is an unexpected chiral heterobimetallic helical chain complex, in which the helical chain consists of the asymmetric unit of [(bpca)Fe(CN)₃Cu(bpca)(H₂O)]. In complex 4, there are two independent trinuclear clusters in one asymmetric unit, and the coordination modes of the two methanol and two water molecules coordinating to the central Mn(II) ion are different (cis and trans). Complex 2 shows metamagnetic behavior with a Neel temperature of T_N = 2.2 K and a critical field of 250 Oe at 1.8 K, where the cyanides mediate the intrachain ferromagnetic coupling between the Cu^II and Fe^III ions. Complex 3 shows ferromagnetic coupling between Cu^II and Fe^III ions, the best-fit for χ_MT versus T using a 1D alternating chain model leads to the parameters J₁ = 7.9(3) cm^-1, J₂ = 1.03(2) cm^-1, and g = 2.196(3). Complex 4 exhibits ferrimagnetic behavior caused by the noncompensation of the local interacting spins (S _Mn = 5/2 and S_Fe = 1/2) which interact antiferromagnetically through bridging cyano groups.

Original language	English
Pages (from-to)	582-590
Number of pages	9
Journal	Inorganic Chemistry
Volume	45
Issue number	2
DOIs	https://doi.org/10.1021/ic0511468
State	Published - 23 Jan 2006
Externally published	Yes

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@article{ebd2226e13bf4eba800f0acb401c0ea6,

title = "Syntheses, structures, and magnetic properties of cyano-bridged heterobimetallic complexes based on [Fe(bpca)(CN)3]-",

abstract = "Two new cyano-bridged one-dimensional heterobimetallic coordination polymers, [(bpca)2FeIII2(CN) 6Cu(H2O)2·1.5H2O] n (2) and [(bpca)FeIII(CN)3Cu(bpca)(H 2O)·H2O]n (3), and a trinuclear complex, [(bpca)2FeIII2(CN)6Mn(CH 3OH)2(H2O)2]·2H2O (4), have been synthesized using the tailored tricyanometalate precursor (Bu4N)[Fe(bpca)(CN)3]·H2O (1) (Bu 4N+ = tetrabutylammonium cation; bpca = bis(2-pyridylcarbonyl)amidate anion) as a building block and structurally characterized. In complex 2, the CuII ions are six-coordinated in an elongated distorted octahedral environment, and they are linked by distorted octahedrons of [Fe(bpca)(CN)3]- to form 1D chain of squares. Complex 3 is an unexpected chiral heterobimetallic helical chain complex, in which the helical chain consists of the asymmetric unit of [(bpca)Fe(CN)3Cu(bpca)(H2O)]. In complex 4, there are two independent trinuclear clusters in one asymmetric unit, and the coordination modes of the two methanol and two water molecules coordinating to the central Mn(II) ion are different (cis and trans). Complex 2 shows metamagnetic behavior with a Neel temperature of TN = 2.2 K and a critical field of 250 Oe at 1.8 K, where the cyanides mediate the intrachain ferromagnetic coupling between the CuII and FeIII ions. Complex 3 shows ferromagnetic coupling between CuII and FeIII ions, the best-fit for χMT versus T using a 1D alternating chain model leads to the parameters J1 = 7.9(3) cm-1, J2 = 1.03(2) cm-1, and g = 2.196(3). Complex 4 exhibits ferrimagnetic behavior caused by the noncompensation of the local interacting spins (S Mn = 5/2 and SFe = 1/2) which interact antiferromagnetically through bridging cyano groups.",

author = "Wen, {He Rui} and Wang, {Cai Feng} and Zuo, {Jing Lin} and You Song and Zeng, {Xi Rui} and You, {Xiao Zeng}",

year = "2006",

month = jan,

day = "23",

doi = "10.1021/ic0511468",

language = "英语",

volume = "45",

pages = "582--590",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "2",

}

TY - JOUR

T1 - Syntheses, structures, and magnetic properties of cyano-bridged heterobimetallic complexes based on [Fe(bpca)(CN)3]-

AU - Wen, He Rui

AU - Wang, Cai Feng

AU - Zuo, Jing Lin

AU - Song, You

AU - Zeng, Xi Rui

AU - You, Xiao Zeng

PY - 2006/1/23

Y1 - 2006/1/23

N2 - Two new cyano-bridged one-dimensional heterobimetallic coordination polymers, [(bpca)2FeIII2(CN) 6Cu(H2O)2·1.5H2O] n (2) and [(bpca)FeIII(CN)3Cu(bpca)(H 2O)·H2O]n (3), and a trinuclear complex, [(bpca)2FeIII2(CN)6Mn(CH 3OH)2(H2O)2]·2H2O (4), have been synthesized using the tailored tricyanometalate precursor (Bu4N)[Fe(bpca)(CN)3]·H2O (1) (Bu 4N+ = tetrabutylammonium cation; bpca = bis(2-pyridylcarbonyl)amidate anion) as a building block and structurally characterized. In complex 2, the CuII ions are six-coordinated in an elongated distorted octahedral environment, and they are linked by distorted octahedrons of [Fe(bpca)(CN)3]- to form 1D chain of squares. Complex 3 is an unexpected chiral heterobimetallic helical chain complex, in which the helical chain consists of the asymmetric unit of [(bpca)Fe(CN)3Cu(bpca)(H2O)]. In complex 4, there are two independent trinuclear clusters in one asymmetric unit, and the coordination modes of the two methanol and two water molecules coordinating to the central Mn(II) ion are different (cis and trans). Complex 2 shows metamagnetic behavior with a Neel temperature of TN = 2.2 K and a critical field of 250 Oe at 1.8 K, where the cyanides mediate the intrachain ferromagnetic coupling between the CuII and FeIII ions. Complex 3 shows ferromagnetic coupling between CuII and FeIII ions, the best-fit for χMT versus T using a 1D alternating chain model leads to the parameters J1 = 7.9(3) cm-1, J2 = 1.03(2) cm-1, and g = 2.196(3). Complex 4 exhibits ferrimagnetic behavior caused by the noncompensation of the local interacting spins (S Mn = 5/2 and SFe = 1/2) which interact antiferromagnetically through bridging cyano groups.

AB - Two new cyano-bridged one-dimensional heterobimetallic coordination polymers, [(bpca)2FeIII2(CN) 6Cu(H2O)2·1.5H2O] n (2) and [(bpca)FeIII(CN)3Cu(bpca)(H 2O)·H2O]n (3), and a trinuclear complex, [(bpca)2FeIII2(CN)6Mn(CH 3OH)2(H2O)2]·2H2O (4), have been synthesized using the tailored tricyanometalate precursor (Bu4N)[Fe(bpca)(CN)3]·H2O (1) (Bu 4N+ = tetrabutylammonium cation; bpca = bis(2-pyridylcarbonyl)amidate anion) as a building block and structurally characterized. In complex 2, the CuII ions are six-coordinated in an elongated distorted octahedral environment, and they are linked by distorted octahedrons of [Fe(bpca)(CN)3]- to form 1D chain of squares. Complex 3 is an unexpected chiral heterobimetallic helical chain complex, in which the helical chain consists of the asymmetric unit of [(bpca)Fe(CN)3Cu(bpca)(H2O)]. In complex 4, there are two independent trinuclear clusters in one asymmetric unit, and the coordination modes of the two methanol and two water molecules coordinating to the central Mn(II) ion are different (cis and trans). Complex 2 shows metamagnetic behavior with a Neel temperature of TN = 2.2 K and a critical field of 250 Oe at 1.8 K, where the cyanides mediate the intrachain ferromagnetic coupling between the CuII and FeIII ions. Complex 3 shows ferromagnetic coupling between CuII and FeIII ions, the best-fit for χMT versus T using a 1D alternating chain model leads to the parameters J1 = 7.9(3) cm-1, J2 = 1.03(2) cm-1, and g = 2.196(3). Complex 4 exhibits ferrimagnetic behavior caused by the noncompensation of the local interacting spins (S Mn = 5/2 and SFe = 1/2) which interact antiferromagnetically through bridging cyano groups.

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U2 - 10.1021/ic0511468

DO - 10.1021/ic0511468

M3 - 文章

AN - SCOPUS:31644443305

SN - 0020-1669

VL - 45

SP - 582

EP - 590

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 2

ER -

Syntheses, structures, and magnetic properties of cyano-bridged heterobimetallic complexes based on [Fe(bpca)(CN)₃]^-

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