Cyanide-bridged Fe(III)-Mn(III) bimetallic systems assembled from the fac -Fe tricyanide and Mn schiff bases: Structures, magnetic properties, and density functional theory calculations

Hyun Young Kwak, Dae Won Ryu, Jin Wuk Lee, Jung Hee Yoon, Hyoung Chan Kim, Eui Kwan Koh, Jamin Krinsky, Chang Seop Hong

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Abstract

Reaction of [(Tp)Fe(CN)3]- [Tp = hydrotris(pyrazolyl) borate] with respective Mn(III) Schiff bases led to the formation of four dimeric molecules, [(Tp)Fe(CN)3][Mn(1-napen)(H2O)] ·MeCN·4H2O [1; 1-napen = N,N′-ethylenebis(2- hydroxy-1-naphthylideneiminato) dianion], [(Tp)Fe(CN)3][Mn(5-Clsalen) (H2O)] [2; 5-Clsalcy = N,N′-(trans-1,2-cyclohexanediylethylene) bis(5-chlorosalicylideneiminato) dianion], [(Tp)Fe(CN)3][Mn(2- acnapen)(MeOH)]·MeOH [3; 2-acnapen = N,N′-ethylenebis(1-hydroxy-2- acetonaphthylideneiminato) dianion], [(Tp)Fe(CN)3][Mn(3-MeOsalen) (H2O)] [4; 3-MeOsalen = N,N′-ethylenebis(3- methoxysalicylideneiminato) dianion], and a one-dimensional (1D) zigzag chain [(Tp)Fe(CN)3][Mn(2-acnapen)]·H2O (5). The dimers contain multiple intermolecular interactions such as hydrogen bonds, face-to-face π-π contacts, and edge-to-face CH-π forces, raising molecular dimensions from one-dimensional (1D) up to three-dimensional (3D) arrays, whereas there are no π-π stacking interactions in the 1D chain compound. Magnetic measurements reveal that ferromagnetic couplings are obviously operative between Mn(III) and Fe(III) spin centers transmitted by CN bridges for 1-3 and 5, and antiferromagnetic interactions are however unexpectedly present in 4. On the basis of the proper spin Hamiltonians, magnetic exchange couplings are estimated to be in the span from 1.79 to 7.48 cm-1 for the ferromagnetically coupled systems and -1.40 cm -1 for the antiferromagnetic dimer. A slow magnetic relaxation is tangible in 5, which is in connection with isolated chains devoid of any intermolecular noncovalent interactions. Density Functional Theory (DFT) calculations and comparison of structural parameters suggest that the observed magnetic behaviors are mainly associated with the bending of the Mn-N-C angle in the bridging pathway.

Original languageEnglish
Pages (from-to)4632-4642
Number of pages11
JournalInorganic Chemistry
Volume49
Issue number10
DOIs
Publication statusPublished - 2010 May 17

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Schiff Bases
Cyanides
cyanides
Dimers
imines
Density functional theory
Hydrogen
Magnetic properties
density functional theory
magnetic properties
Magnetic relaxation
Hamiltonians
Exchange coupling
Magnetic variables measurement
Hydrogen bonds
dimers
interactions
Molecules
magnetic relaxation
borates

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Cyanide-bridged Fe(III)-Mn(III) bimetallic systems assembled from the fac -Fe tricyanide and Mn schiff bases : Structures, magnetic properties, and density functional theory calculations. / Kwak, Hyun Young; Ryu, Dae Won; Lee, Jin Wuk; Yoon, Jung Hee; Kim, Hyoung Chan; Koh, Eui Kwan; Krinsky, Jamin; Hong, Chang Seop.

In: Inorganic Chemistry, Vol. 49, No. 10, 17.05.2010, p. 4632-4642.

Research output: Contribution to journalArticle

Kwak, Hyun Young ; Ryu, Dae Won ; Lee, Jin Wuk ; Yoon, Jung Hee ; Kim, Hyoung Chan ; Koh, Eui Kwan ; Krinsky, Jamin ; Hong, Chang Seop. / Cyanide-bridged Fe(III)-Mn(III) bimetallic systems assembled from the fac -Fe tricyanide and Mn schiff bases : Structures, magnetic properties, and density functional theory calculations. In: Inorganic Chemistry. 2010 ; Vol. 49, No. 10. pp. 4632-4642.
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title = "Cyanide-bridged Fe(III)-Mn(III) bimetallic systems assembled from the fac -Fe tricyanide and Mn schiff bases: Structures, magnetic properties, and density functional theory calculations",
abstract = "Reaction of [(Tp)Fe(CN)3]- [Tp = hydrotris(pyrazolyl) borate] with respective Mn(III) Schiff bases led to the formation of four dimeric molecules, [(Tp)Fe(CN)3][Mn(1-napen)(H2O)] ·MeCN·4H2O [1; 1-napen = N,N′-ethylenebis(2- hydroxy-1-naphthylideneiminato) dianion], [(Tp)Fe(CN)3][Mn(5-Clsalen) (H2O)] [2; 5-Clsalcy = N,N′-(trans-1,2-cyclohexanediylethylene) bis(5-chlorosalicylideneiminato) dianion], [(Tp)Fe(CN)3][Mn(2- acnapen)(MeOH)]·MeOH [3; 2-acnapen = N,N′-ethylenebis(1-hydroxy-2- acetonaphthylideneiminato) dianion], [(Tp)Fe(CN)3][Mn(3-MeOsalen) (H2O)] [4; 3-MeOsalen = N,N′-ethylenebis(3- methoxysalicylideneiminato) dianion], and a one-dimensional (1D) zigzag chain [(Tp)Fe(CN)3][Mn(2-acnapen)]·H2O (5). The dimers contain multiple intermolecular interactions such as hydrogen bonds, face-to-face π-π contacts, and edge-to-face CH-π forces, raising molecular dimensions from one-dimensional (1D) up to three-dimensional (3D) arrays, whereas there are no π-π stacking interactions in the 1D chain compound. Magnetic measurements reveal that ferromagnetic couplings are obviously operative between Mn(III) and Fe(III) spin centers transmitted by CN bridges for 1-3 and 5, and antiferromagnetic interactions are however unexpectedly present in 4. On the basis of the proper spin Hamiltonians, magnetic exchange couplings are estimated to be in the span from 1.79 to 7.48 cm-1 for the ferromagnetically coupled systems and -1.40 cm -1 for the antiferromagnetic dimer. A slow magnetic relaxation is tangible in 5, which is in connection with isolated chains devoid of any intermolecular noncovalent interactions. Density Functional Theory (DFT) calculations and comparison of structural parameters suggest that the observed magnetic behaviors are mainly associated with the bending of the Mn-N-C angle in the bridging pathway.",
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T1 - Cyanide-bridged Fe(III)-Mn(III) bimetallic systems assembled from the fac -Fe tricyanide and Mn schiff bases

T2 - Structures, magnetic properties, and density functional theory calculations

AU - Kwak, Hyun Young

AU - Ryu, Dae Won

AU - Lee, Jin Wuk

AU - Yoon, Jung Hee

AU - Kim, Hyoung Chan

AU - Koh, Eui Kwan

AU - Krinsky, Jamin

AU - Hong, Chang Seop

PY - 2010/5/17

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N2 - Reaction of [(Tp)Fe(CN)3]- [Tp = hydrotris(pyrazolyl) borate] with respective Mn(III) Schiff bases led to the formation of four dimeric molecules, [(Tp)Fe(CN)3][Mn(1-napen)(H2O)] ·MeCN·4H2O [1; 1-napen = N,N′-ethylenebis(2- hydroxy-1-naphthylideneiminato) dianion], [(Tp)Fe(CN)3][Mn(5-Clsalen) (H2O)] [2; 5-Clsalcy = N,N′-(trans-1,2-cyclohexanediylethylene) bis(5-chlorosalicylideneiminato) dianion], [(Tp)Fe(CN)3][Mn(2- acnapen)(MeOH)]·MeOH [3; 2-acnapen = N,N′-ethylenebis(1-hydroxy-2- acetonaphthylideneiminato) dianion], [(Tp)Fe(CN)3][Mn(3-MeOsalen) (H2O)] [4; 3-MeOsalen = N,N′-ethylenebis(3- methoxysalicylideneiminato) dianion], and a one-dimensional (1D) zigzag chain [(Tp)Fe(CN)3][Mn(2-acnapen)]·H2O (5). The dimers contain multiple intermolecular interactions such as hydrogen bonds, face-to-face π-π contacts, and edge-to-face CH-π forces, raising molecular dimensions from one-dimensional (1D) up to three-dimensional (3D) arrays, whereas there are no π-π stacking interactions in the 1D chain compound. Magnetic measurements reveal that ferromagnetic couplings are obviously operative between Mn(III) and Fe(III) spin centers transmitted by CN bridges for 1-3 and 5, and antiferromagnetic interactions are however unexpectedly present in 4. On the basis of the proper spin Hamiltonians, magnetic exchange couplings are estimated to be in the span from 1.79 to 7.48 cm-1 for the ferromagnetically coupled systems and -1.40 cm -1 for the antiferromagnetic dimer. A slow magnetic relaxation is tangible in 5, which is in connection with isolated chains devoid of any intermolecular noncovalent interactions. Density Functional Theory (DFT) calculations and comparison of structural parameters suggest that the observed magnetic behaviors are mainly associated with the bending of the Mn-N-C angle in the bridging pathway.

AB - Reaction of [(Tp)Fe(CN)3]- [Tp = hydrotris(pyrazolyl) borate] with respective Mn(III) Schiff bases led to the formation of four dimeric molecules, [(Tp)Fe(CN)3][Mn(1-napen)(H2O)] ·MeCN·4H2O [1; 1-napen = N,N′-ethylenebis(2- hydroxy-1-naphthylideneiminato) dianion], [(Tp)Fe(CN)3][Mn(5-Clsalen) (H2O)] [2; 5-Clsalcy = N,N′-(trans-1,2-cyclohexanediylethylene) bis(5-chlorosalicylideneiminato) dianion], [(Tp)Fe(CN)3][Mn(2- acnapen)(MeOH)]·MeOH [3; 2-acnapen = N,N′-ethylenebis(1-hydroxy-2- acetonaphthylideneiminato) dianion], [(Tp)Fe(CN)3][Mn(3-MeOsalen) (H2O)] [4; 3-MeOsalen = N,N′-ethylenebis(3- methoxysalicylideneiminato) dianion], and a one-dimensional (1D) zigzag chain [(Tp)Fe(CN)3][Mn(2-acnapen)]·H2O (5). The dimers contain multiple intermolecular interactions such as hydrogen bonds, face-to-face π-π contacts, and edge-to-face CH-π forces, raising molecular dimensions from one-dimensional (1D) up to three-dimensional (3D) arrays, whereas there are no π-π stacking interactions in the 1D chain compound. Magnetic measurements reveal that ferromagnetic couplings are obviously operative between Mn(III) and Fe(III) spin centers transmitted by CN bridges for 1-3 and 5, and antiferromagnetic interactions are however unexpectedly present in 4. On the basis of the proper spin Hamiltonians, magnetic exchange couplings are estimated to be in the span from 1.79 to 7.48 cm-1 for the ferromagnetically coupled systems and -1.40 cm -1 for the antiferromagnetic dimer. A slow magnetic relaxation is tangible in 5, which is in connection with isolated chains devoid of any intermolecular noncovalent interactions. Density Functional Theory (DFT) calculations and comparison of structural parameters suggest that the observed magnetic behaviors are mainly associated with the bending of the Mn-N-C angle in the bridging pathway.

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