Two-dimensional coordination polymers with one-dimensional magnetic chains

Hydrothermal synthesis, crystal structure, and magnetic and thermal properties of∞ 2 [MCl2(4,4′-bipyridine)] (M = Fe, Co, Ni, Co/Ni)

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Abstract

Two-dimensional transition-metal coordination polymers 2[MCl2(bpy)] (M = Fe, Co, Ni; Co/Ni, bpy = 4, 4′-bipyridine) have been synthesized in superheated water solutions. The hydrothermal routes resulted in four compounds 2[FeCl2(bpy)](I), 2[CoCl2(bpy)](II), 2[NiCl2(bpy)](III), and 2[(Co/Ni)Cl2(bpy)](IV). Compounds I-IV are isostructural and belong to orthorhombic crystal system, space group Cmmm (No. 65). Crystal data for I: a = 11.929(2) Å, b = 11.447(2) Å, c = 3.638(1) Å, V = 496.77(18) Å3, Z = 2. Crystal data for II: a = 11.993(2) Å, b = 11.374(2) Å, c = 3.611(1) Å, V = 492.57(18) Å3, Z = 2. The structure is a noninterpenetrating two-dimensional network containing transition-metal centers octahedrally coordinated by four bridging chlorine and two bpy ligands at trans positions. The adjacent bpy ligands within a single layer are parallel to each other at a distance of 3.6 Å. Spontaneous antiferromagnetic ordering was found in all compounds from the magnetic susceptibility x(T) measurements under low fields. The transition temperatures are 10.0, 5.0, 8.5, and 7.5 K, for I, II, III, and IV, respectively. The μeff values yielded from fitting the high temperature x(T) indicate the high spin states of metal ions. In addition, a metamagnetic transition was observed in the field-dependent magnetization measurement for all four compounds. The magnetic properties observed in this system are attributed to the ferromagnetic intrachain M-M exchange interaction through the Cl2 bridges along the c axis and the antiferromagnetic interchain interaction between the M ions. TGA studies indicate that all four compounds are thermally stable with an on-set temperature of weight loss greater than 400 °C.

Original languageEnglish
Pages (from-to)5410-5414
Number of pages5
JournalInorganic Chemistry
Volume38
Issue number23
Publication statusPublished - 1999

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Hydrothermal synthesis
coordination polymers
Magnetic properties
Polymers
Thermodynamic properties
thermodynamic properties
Crystal structure
magnetic properties
Crystals
crystal structure
Transition metals
synthesis
transition metals
Ligands
crystals
ligands
Chlorine
Exchange interactions
Magnetic susceptibility
chlorine

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{df4bf041ca0e4ca888b1eece5d7ddf5a,
title = "Two-dimensional coordination polymers with one-dimensional magnetic chains: Hydrothermal synthesis, crystal structure, and magnetic and thermal properties of∞ 2 [MCl2(4,4′-bipyridine)] (M = Fe, Co, Ni, Co/Ni)",
abstract = "Two-dimensional transition-metal coordination polymers ∞ 2[MCl2(bpy)] (M = Fe, Co, Ni; Co/Ni, bpy = 4, 4′-bipyridine) have been synthesized in superheated water solutions. The hydrothermal routes resulted in four compounds ∞ 2[FeCl2(bpy)](I), ∞ 2[CoCl2(bpy)](II), ∞ 2[NiCl2(bpy)](III), and ∞ 2[(Co/Ni)Cl2(bpy)](IV). Compounds I-IV are isostructural and belong to orthorhombic crystal system, space group Cmmm (No. 65). Crystal data for I: a = 11.929(2) {\AA}, b = 11.447(2) {\AA}, c = 3.638(1) {\AA}, V = 496.77(18) {\AA}3, Z = 2. Crystal data for II: a = 11.993(2) {\AA}, b = 11.374(2) {\AA}, c = 3.611(1) {\AA}, V = 492.57(18) {\AA}3, Z = 2. The structure is a noninterpenetrating two-dimensional network containing transition-metal centers octahedrally coordinated by four bridging chlorine and two bpy ligands at trans positions. The adjacent bpy ligands within a single layer are parallel to each other at a distance of 3.6 {\AA}. Spontaneous antiferromagnetic ordering was found in all compounds from the magnetic susceptibility x(T) measurements under low fields. The transition temperatures are 10.0, 5.0, 8.5, and 7.5 K, for I, II, III, and IV, respectively. The μeff values yielded from fitting the high temperature x(T) indicate the high spin states of metal ions. In addition, a metamagnetic transition was observed in the field-dependent magnetization measurement for all four compounds. The magnetic properties observed in this system are attributed to the ferromagnetic intrachain M-M exchange interaction through the Cl2 bridges along the c axis and the antiferromagnetic interchain interaction between the M ions. TGA studies indicate that all four compounds are thermally stable with an on-set temperature of weight loss greater than 400 °C.",
author = "Jing Li",
year = "1999",
language = "English",
volume = "38",
pages = "5410--5414",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "23",

}

TY - JOUR

T1 - Two-dimensional coordination polymers with one-dimensional magnetic chains

T2 - Hydrothermal synthesis, crystal structure, and magnetic and thermal properties of∞ 2 [MCl2(4,4′-bipyridine)] (M = Fe, Co, Ni, Co/Ni)

AU - Li, Jing

PY - 1999

Y1 - 1999

N2 - Two-dimensional transition-metal coordination polymers ∞ 2[MCl2(bpy)] (M = Fe, Co, Ni; Co/Ni, bpy = 4, 4′-bipyridine) have been synthesized in superheated water solutions. The hydrothermal routes resulted in four compounds ∞ 2[FeCl2(bpy)](I), ∞ 2[CoCl2(bpy)](II), ∞ 2[NiCl2(bpy)](III), and ∞ 2[(Co/Ni)Cl2(bpy)](IV). Compounds I-IV are isostructural and belong to orthorhombic crystal system, space group Cmmm (No. 65). Crystal data for I: a = 11.929(2) Å, b = 11.447(2) Å, c = 3.638(1) Å, V = 496.77(18) Å3, Z = 2. Crystal data for II: a = 11.993(2) Å, b = 11.374(2) Å, c = 3.611(1) Å, V = 492.57(18) Å3, Z = 2. The structure is a noninterpenetrating two-dimensional network containing transition-metal centers octahedrally coordinated by four bridging chlorine and two bpy ligands at trans positions. The adjacent bpy ligands within a single layer are parallel to each other at a distance of 3.6 Å. Spontaneous antiferromagnetic ordering was found in all compounds from the magnetic susceptibility x(T) measurements under low fields. The transition temperatures are 10.0, 5.0, 8.5, and 7.5 K, for I, II, III, and IV, respectively. The μeff values yielded from fitting the high temperature x(T) indicate the high spin states of metal ions. In addition, a metamagnetic transition was observed in the field-dependent magnetization measurement for all four compounds. The magnetic properties observed in this system are attributed to the ferromagnetic intrachain M-M exchange interaction through the Cl2 bridges along the c axis and the antiferromagnetic interchain interaction between the M ions. TGA studies indicate that all four compounds are thermally stable with an on-set temperature of weight loss greater than 400 °C.

AB - Two-dimensional transition-metal coordination polymers ∞ 2[MCl2(bpy)] (M = Fe, Co, Ni; Co/Ni, bpy = 4, 4′-bipyridine) have been synthesized in superheated water solutions. The hydrothermal routes resulted in four compounds ∞ 2[FeCl2(bpy)](I), ∞ 2[CoCl2(bpy)](II), ∞ 2[NiCl2(bpy)](III), and ∞ 2[(Co/Ni)Cl2(bpy)](IV). Compounds I-IV are isostructural and belong to orthorhombic crystal system, space group Cmmm (No. 65). Crystal data for I: a = 11.929(2) Å, b = 11.447(2) Å, c = 3.638(1) Å, V = 496.77(18) Å3, Z = 2. Crystal data for II: a = 11.993(2) Å, b = 11.374(2) Å, c = 3.611(1) Å, V = 492.57(18) Å3, Z = 2. The structure is a noninterpenetrating two-dimensional network containing transition-metal centers octahedrally coordinated by four bridging chlorine and two bpy ligands at trans positions. The adjacent bpy ligands within a single layer are parallel to each other at a distance of 3.6 Å. Spontaneous antiferromagnetic ordering was found in all compounds from the magnetic susceptibility x(T) measurements under low fields. The transition temperatures are 10.0, 5.0, 8.5, and 7.5 K, for I, II, III, and IV, respectively. The μeff values yielded from fitting the high temperature x(T) indicate the high spin states of metal ions. In addition, a metamagnetic transition was observed in the field-dependent magnetization measurement for all four compounds. The magnetic properties observed in this system are attributed to the ferromagnetic intrachain M-M exchange interaction through the Cl2 bridges along the c axis and the antiferromagnetic interchain interaction between the M ions. TGA studies indicate that all four compounds are thermally stable with an on-set temperature of weight loss greater than 400 °C.

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