Bimetallic MV 2CuII 3 (M = Mo, W) coordination complexes based on octacyanometalates: Structures and magnetic variations tuned by chelated tetradentate macrocyclic ligands

Hak Lim Jeong, Sin You Young, Sik Yoo Houng, Hee Yoon Jung, Il Kim Jae, Kwan Kon Eui, Chang Seop Hong

Research output: Contribution to journalArticle

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Abstract

Four octacyanometalate-based bimetallic Cu-M (M = Mo, W) assemblies coordinated by tetradentate macrocyclic ligands were prepared via self-assembly process in a stoichiometric ratio of [M(CN)8]3- and Cu(macrocycle)2+ and characterized in terms of structures and magnetic properties. The crystal structures are varied depending on the macrocycles used. The employment of cyclam with no pendant groups produced a one-dimensional chain (1) with a rope-ladder pattern, whereas macrocycles with side groups allowed for the formation of two-dimensional honeycomb-like architectures (2-4). From the crystal structures, the variations in apical Cu-Nax lengths and Cu-Nax-Cax angles on the bridging pathways are observed, which arises from the existence of side groups on macrocyclic ligands. The magnetic results reveal that all of the prepared compounds show ferromagnetic couplings between magnetic centers transmitted through CN bridges under the present structural parameters. Comparing the magnetic strength of the Cu-Mo (3d-4d; 2) and Cu-W (3d-5d; 3) complexes supports that 3d-5d magnetic coupling is stronger than 3d-4d because the 5d orbital is more diffuse than 4d. The magnetic analyses for 1-4 and related complexes tentatively suggest that, when the Cu-Nax distances are long enough, the axial Cu-Nax bond length in the bridging route may be one of the major structural parameters to determine the magnitude of the ferromagnetic exchange coupling.

Original languageEnglish
Pages (from-to)10578-10586
Number of pages9
JournalInorganic Chemistry
Volume46
Issue number25
DOIs
Publication statusPublished - 2007 Dec 10

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magnetic variations
Magnetic couplings
Coordination Complexes
Crystal structure
Ligands
Exchange coupling
ligands
Ladders
Bond length
Self assembly
Magnetic properties
crystal structure
ladders
assemblies
self assembly
routes
magnetic properties
orbitals
cyclam

ASJC Scopus subject areas

  • Inorganic Chemistry

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Bimetallic MV 2CuII 3 (M = Mo, W) coordination complexes based on octacyanometalates : Structures and magnetic variations tuned by chelated tetradentate macrocyclic ligands. / Jeong, Hak Lim; Young, Sin You; Houng, Sik Yoo; Jung, Hee Yoon; Jae, Il Kim; Eui, Kwan Kon; Hong, Chang Seop.

In: Inorganic Chemistry, Vol. 46, No. 25, 10.12.2007, p. 10578-10586.

Research output: Contribution to journalArticle

Jeong, Hak Lim ; Young, Sin You ; Houng, Sik Yoo ; Jung, Hee Yoon ; Jae, Il Kim ; Eui, Kwan Kon ; Hong, Chang Seop. / Bimetallic MV 2CuII 3 (M = Mo, W) coordination complexes based on octacyanometalates : Structures and magnetic variations tuned by chelated tetradentate macrocyclic ligands. In: Inorganic Chemistry. 2007 ; Vol. 46, No. 25. pp. 10578-10586.
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abstract = "Four octacyanometalate-based bimetallic Cu-M (M = Mo, W) assemblies coordinated by tetradentate macrocyclic ligands were prepared via self-assembly process in a stoichiometric ratio of [M(CN)8]3- and Cu(macrocycle)2+ and characterized in terms of structures and magnetic properties. The crystal structures are varied depending on the macrocycles used. The employment of cyclam with no pendant groups produced a one-dimensional chain (1) with a rope-ladder pattern, whereas macrocycles with side groups allowed for the formation of two-dimensional honeycomb-like architectures (2-4). From the crystal structures, the variations in apical Cu-Nax lengths and Cu-Nax-Cax angles on the bridging pathways are observed, which arises from the existence of side groups on macrocyclic ligands. The magnetic results reveal that all of the prepared compounds show ferromagnetic couplings between magnetic centers transmitted through CN bridges under the present structural parameters. Comparing the magnetic strength of the Cu-Mo (3d-4d; 2) and Cu-W (3d-5d; 3) complexes supports that 3d-5d magnetic coupling is stronger than 3d-4d because the 5d orbital is more diffuse than 4d. The magnetic analyses for 1-4 and related complexes tentatively suggest that, when the Cu-Nax distances are long enough, the axial Cu-Nax bond length in the bridging route may be one of the major structural parameters to determine the magnitude of the ferromagnetic exchange coupling.",
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