[Fe(bpb)(CN)2]- as a versatile building block for the design of novel low-dimensional heterobimetallic systems: Synthesis, crystal structures, and magnetic properties of cyano-bridged FeIII-Ni II complexes [(bpb)2- = 1,2-bis(pyridine-2-carboxamido) benzenate]

Zhong Hai Ni, Hui Zhong Kou, Yi Hua Zhao, Lei Zheng, Ru Ji Wang, Ai Li Cui, Osamu Sato

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Abstract

A dicyano-containing [Fe(bpb)(CN)2]- building block has been employed for the synthesis of cyano-bridged heterometallic Ni II-FeIII complexes. The presence of steric bpb 2- ligand around the iron ion results in the formation of low-dimensional species: five are neutral NiFe2 trimers and three are one-dimensional (1D). The structure of the 1D complexes consists of alternating [NiL]2+ and [Fe(bpb)(CN)2]- generating a cyano-bridged cationic polymeric chain and the perchlorate as the counteranion. In all complexes, the coordination geometry of the nickel ions is approximately octahedral with the cyano nitrogen atoms at the trans positions. Magnetic studies of seven complexes show the presence of ferromagnetic interaction between the metal ions through the cyano bridges. Variable temperature magnetic susceptibility investigations of the trimeric complexes yield the following JNiFe values (based on the spin exchange Hamiltonian H =-2J NiFeSNi(SFe(1) + SFe(2)): J NiFe = 6.40(5), 7.8(1), 8.9(2), and 6.03(4) cm-1, respectively. The study of the magneto-structural correlation reveals that the cyanide-bridging bond angle is related to the strength of magnetic exchange coupling: the larger the Ni-N≡C bond angle, the stronger the Ni⋯Fe magnetic interaction. One 1D complex exhibits long-range antiferromagnetic ordering with TN = 3.5 K. Below TN (1.82 K), a metamagnetic behavior was observed with the critical field of ∼6 kOe. The present research shows that the [Fe(bpb)(CN)2]- building block is a good candidate for the construction of low-dimensional magnetic materials.

Original languageEnglish
Pages (from-to)2050-2059
Number of pages10
JournalInorganic chemistry
Volume44
Issue number6
DOIs
Publication statusPublished - Mar 21 2005
Externally publishedYes

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pyridines
Magnetic properties
Crystal structure
Ions
magnetic properties
Hamiltonians
Exchange coupling
crystal structure
spin exchange
Magnetic materials
Coordination Complexes
Cyanides
cyanides
synthesis
perchlorates
trimers
magnetic materials
Nickel
Magnetic susceptibility
nitrogen atoms

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

@article{86e6f4f7aca448a4947f5adb907ab7d5,
title = "[Fe(bpb)(CN)2]- as a versatile building block for the design of novel low-dimensional heterobimetallic systems: Synthesis, crystal structures, and magnetic properties of cyano-bridged FeIII-Ni II complexes [(bpb)2- = 1,2-bis(pyridine-2-carboxamido) benzenate]",
abstract = "A dicyano-containing [Fe(bpb)(CN)2]- building block has been employed for the synthesis of cyano-bridged heterometallic Ni II-FeIII complexes. The presence of steric bpb 2- ligand around the iron ion results in the formation of low-dimensional species: five are neutral NiFe2 trimers and three are one-dimensional (1D). The structure of the 1D complexes consists of alternating [NiL]2+ and [Fe(bpb)(CN)2]- generating a cyano-bridged cationic polymeric chain and the perchlorate as the counteranion. In all complexes, the coordination geometry of the nickel ions is approximately octahedral with the cyano nitrogen atoms at the trans positions. Magnetic studies of seven complexes show the presence of ferromagnetic interaction between the metal ions through the cyano bridges. Variable temperature magnetic susceptibility investigations of the trimeric complexes yield the following JNiFe values (based on the spin exchange Hamiltonian H =-2J NiFeSNi(SFe(1) + SFe(2)): J NiFe = 6.40(5), 7.8(1), 8.9(2), and 6.03(4) cm-1, respectively. The study of the magneto-structural correlation reveals that the cyanide-bridging bond angle is related to the strength of magnetic exchange coupling: the larger the Ni-N≡C bond angle, the stronger the Ni⋯Fe magnetic interaction. One 1D complex exhibits long-range antiferromagnetic ordering with TN = 3.5 K. Below TN (1.82 K), a metamagnetic behavior was observed with the critical field of ∼6 kOe. The present research shows that the [Fe(bpb)(CN)2]- building block is a good candidate for the construction of low-dimensional magnetic materials.",
author = "Ni, {Zhong Hai} and Kou, {Hui Zhong} and Zhao, {Yi Hua} and Lei Zheng and Wang, {Ru Ji} and Cui, {Ai Li} and Osamu Sato",
year = "2005",
month = "3",
day = "21",
doi = "10.1021/ic0489903",
language = "English",
volume = "44",
pages = "2050--2059",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "6",

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TY - JOUR

T1 - [Fe(bpb)(CN)2]- as a versatile building block for the design of novel low-dimensional heterobimetallic systems

T2 - Synthesis, crystal structures, and magnetic properties of cyano-bridged FeIII-Ni II complexes [(bpb)2- = 1,2-bis(pyridine-2-carboxamido) benzenate]

AU - Ni, Zhong Hai

AU - Kou, Hui Zhong

AU - Zhao, Yi Hua

AU - Zheng, Lei

AU - Wang, Ru Ji

AU - Cui, Ai Li

AU - Sato, Osamu

PY - 2005/3/21

Y1 - 2005/3/21

N2 - A dicyano-containing [Fe(bpb)(CN)2]- building block has been employed for the synthesis of cyano-bridged heterometallic Ni II-FeIII complexes. The presence of steric bpb 2- ligand around the iron ion results in the formation of low-dimensional species: five are neutral NiFe2 trimers and three are one-dimensional (1D). The structure of the 1D complexes consists of alternating [NiL]2+ and [Fe(bpb)(CN)2]- generating a cyano-bridged cationic polymeric chain and the perchlorate as the counteranion. In all complexes, the coordination geometry of the nickel ions is approximately octahedral with the cyano nitrogen atoms at the trans positions. Magnetic studies of seven complexes show the presence of ferromagnetic interaction between the metal ions through the cyano bridges. Variable temperature magnetic susceptibility investigations of the trimeric complexes yield the following JNiFe values (based on the spin exchange Hamiltonian H =-2J NiFeSNi(SFe(1) + SFe(2)): J NiFe = 6.40(5), 7.8(1), 8.9(2), and 6.03(4) cm-1, respectively. The study of the magneto-structural correlation reveals that the cyanide-bridging bond angle is related to the strength of magnetic exchange coupling: the larger the Ni-N≡C bond angle, the stronger the Ni⋯Fe magnetic interaction. One 1D complex exhibits long-range antiferromagnetic ordering with TN = 3.5 K. Below TN (1.82 K), a metamagnetic behavior was observed with the critical field of ∼6 kOe. The present research shows that the [Fe(bpb)(CN)2]- building block is a good candidate for the construction of low-dimensional magnetic materials.

AB - A dicyano-containing [Fe(bpb)(CN)2]- building block has been employed for the synthesis of cyano-bridged heterometallic Ni II-FeIII complexes. The presence of steric bpb 2- ligand around the iron ion results in the formation of low-dimensional species: five are neutral NiFe2 trimers and three are one-dimensional (1D). The structure of the 1D complexes consists of alternating [NiL]2+ and [Fe(bpb)(CN)2]- generating a cyano-bridged cationic polymeric chain and the perchlorate as the counteranion. In all complexes, the coordination geometry of the nickel ions is approximately octahedral with the cyano nitrogen atoms at the trans positions. Magnetic studies of seven complexes show the presence of ferromagnetic interaction between the metal ions through the cyano bridges. Variable temperature magnetic susceptibility investigations of the trimeric complexes yield the following JNiFe values (based on the spin exchange Hamiltonian H =-2J NiFeSNi(SFe(1) + SFe(2)): J NiFe = 6.40(5), 7.8(1), 8.9(2), and 6.03(4) cm-1, respectively. The study of the magneto-structural correlation reveals that the cyanide-bridging bond angle is related to the strength of magnetic exchange coupling: the larger the Ni-N≡C bond angle, the stronger the Ni⋯Fe magnetic interaction. One 1D complex exhibits long-range antiferromagnetic ordering with TN = 3.5 K. Below TN (1.82 K), a metamagnetic behavior was observed with the critical field of ∼6 kOe. The present research shows that the [Fe(bpb)(CN)2]- building block is a good candidate for the construction of low-dimensional magnetic materials.

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U2 - 10.1021/ic0489903

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JF - Inorganic Chemistry

SN - 0020-1669

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