Syntheses, crystal structures and magnetic properties of cyano- and phenoxide-bridged Fe(iii)Mn(iii) tetramers containing fac-Fe(iii) tricyanides and Mn(iii) Schiff bases

Hyun Young Kwak; Dae Won Ryu; Hyoung Chan Kim; Eui Kwan Koh; Beong Ki Cho; Chang Seop Hong

doi:10.1039/b818559j

Syntheses, crystal structures and magnetic properties of cyano- and phenoxide-bridged Fe(iii)Mn(iii) tetramers containing fac-Fe(iii) tricyanides and Mn(iii) Schiff bases

Hyun Young Kwak, Dae Won Ryu, Hyoung Chan Kim, Eui Kwan Koh, Beong Ki Cho, Chang Seop Hong

Department of Chemistry

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Abstract

Three cyanide-linked Fe(iii)Mn(iii) bimetallic clusters, [(Tp)Fe(CN) ₃]₂[Mn(acphen)]₂ [1; acphen = N,N′-ethylenebis(2-hydroxyacetophenylideneiminato) dianion], [(Tp)Fe(CN)₃]₂[Mn(5-Bracphen)]₂ [2; 5-Bracphen = N,N′-ethylenebis(5-bromo-2-hydroxyacetophenylideneiminato) dianion], and [(Tp)Fe(CN)₃]₂[Mn(salen)]₂·6H ₂O [3; salen = N,N′-ethylenebis(salicylidineiminato) dianion], were prepared by self-assembling a facial [(Tp)Fe(CN)₃]^- [Tp = hydrotris(pyrazolyl)borate] precursor and respective Mn(iii) Schiff bases. X-Ray crystal structure analyses revealed that each complex is composed of a central Mn(iii) dimer doubly linked by phenoxides of the tetradentate N ₂O₂ Schiff bases and the terminal [(Tp)Fe(CN) ₃]^- groups connecting to the center through cyanides. Using the spin Hamiltonian H = -2J₁(S_Fe1·S _Mn1 + S_Mn1a·S_Fe1a) - 2J ₂(S_Mn1·S_Mn1a), where J₁ stands for the exchange coupling constant between Fe(iii) (S_Fe = 1/2) and Mn(iii) (S_Mn = 2) through cyanides and J₂ between Mn(iii) ions via phenoxides, the best fits corresponded to J₁ = 2.61 cm^-1 and J₂ = 0.85 cm^-1 for 1, J₁ = 2.50 cm^-1 and J₂ = 1.30 cm^-1 for 2, and J ₁ = -2.15 cm^-1 and J₂ = 0.55 cm^-1 for 3. The phenoxide routes transmit ferromagnetic interactions in all cases, while ferromagnetic or antiferromagnetic couplings occur through the cyanide linkage. Although the geometric parameters relevant to the magnetic Fe-CN-Mn pathways are analogous to each other their magnetic natures are varied across the compounds, which supports that a degree of orbital overlap is quite sensitive to a subtle structural change in the present system.

Original language	English
Pages (from-to)	1954-1961
Number of pages	8
Journal	Dalton Transactions
Issue number	11
DOIs	https://doi.org/10.1039/b818559j
Publication status	Published - 2009

ASJC Scopus subject areas

Inorganic Chemistry

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@article{957bdd0e909f41829ac6c10f395b137d,

title = "Syntheses, crystal structures and magnetic properties of cyano- and phenoxide-bridged Fe(iii)Mn(iii) tetramers containing fac-Fe(iii) tricyanides and Mn(iii) Schiff bases",

abstract = "Three cyanide-linked Fe(iii)Mn(iii) bimetallic clusters, [(Tp)Fe(CN) 3]2[Mn(acphen)]2 [1; acphen = N,N′-ethylenebis(2-hydroxyacetophenylideneiminato) dianion], [(Tp)Fe(CN)3]2[Mn(5-Bracphen)]2 [2; 5-Bracphen = N,N′-ethylenebis(5-bromo-2-hydroxyacetophenylideneiminato) dianion], and [(Tp)Fe(CN)3]2[Mn(salen)]2·6H 2O [3; salen = N,N′-ethylenebis(salicylidineiminato) dianion], were prepared by self-assembling a facial [(Tp)Fe(CN)3]- [Tp = hydrotris(pyrazolyl)borate] precursor and respective Mn(iii) Schiff bases. X-Ray crystal structure analyses revealed that each complex is composed of a central Mn(iii) dimer doubly linked by phenoxides of the tetradentate N 2O2 Schiff bases and the terminal [(Tp)Fe(CN) 3]- groups connecting to the center through cyanides. Using the spin Hamiltonian H = -2J1(SFe1·S Mn1 + SMn1a·SFe1a) - 2J 2(SMn1·SMn1a), where J1 stands for the exchange coupling constant between Fe(iii) (SFe = 1/2) and Mn(iii) (SMn = 2) through cyanides and J2 between Mn(iii) ions via phenoxides, the best fits corresponded to J1 = 2.61 cm-1 and J2 = 0.85 cm-1 for 1, J1 = 2.50 cm-1 and J2 = 1.30 cm-1 for 2, and J 1 = -2.15 cm-1 and J2 = 0.55 cm-1 for 3. The phenoxide routes transmit ferromagnetic interactions in all cases, while ferromagnetic or antiferromagnetic couplings occur through the cyanide linkage. Although the geometric parameters relevant to the magnetic Fe-CN-Mn pathways are analogous to each other their magnetic natures are varied across the compounds, which supports that a degree of orbital overlap is quite sensitive to a subtle structural change in the present system.",

author = "Kwak, {Hyun Young} and Ryu, {Dae Won} and Kim, {Hyoung Chan} and Koh, {Eui Kwan} and Cho, {Beong Ki} and Hong, {Chang Seop}",

year = "2009",

doi = "10.1039/b818559j",

language = "English",

pages = "1954--1961",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "11",

}

TY - JOUR

T1 - Syntheses, crystal structures and magnetic properties of cyano- and phenoxide-bridged Fe(iii)Mn(iii) tetramers containing fac-Fe(iii) tricyanides and Mn(iii) Schiff bases

AU - Kwak, Hyun Young

AU - Ryu, Dae Won

AU - Kim, Hyoung Chan

AU - Koh, Eui Kwan

AU - Cho, Beong Ki

AU - Hong, Chang Seop

PY - 2009

Y1 - 2009

N2 - Three cyanide-linked Fe(iii)Mn(iii) bimetallic clusters, [(Tp)Fe(CN) 3]2[Mn(acphen)]2 [1; acphen = N,N′-ethylenebis(2-hydroxyacetophenylideneiminato) dianion], [(Tp)Fe(CN)3]2[Mn(5-Bracphen)]2 [2; 5-Bracphen = N,N′-ethylenebis(5-bromo-2-hydroxyacetophenylideneiminato) dianion], and [(Tp)Fe(CN)3]2[Mn(salen)]2·6H 2O [3; salen = N,N′-ethylenebis(salicylidineiminato) dianion], were prepared by self-assembling a facial [(Tp)Fe(CN)3]- [Tp = hydrotris(pyrazolyl)borate] precursor and respective Mn(iii) Schiff bases. X-Ray crystal structure analyses revealed that each complex is composed of a central Mn(iii) dimer doubly linked by phenoxides of the tetradentate N 2O2 Schiff bases and the terminal [(Tp)Fe(CN) 3]- groups connecting to the center through cyanides. Using the spin Hamiltonian H = -2J1(SFe1·S Mn1 + SMn1a·SFe1a) - 2J 2(SMn1·SMn1a), where J1 stands for the exchange coupling constant between Fe(iii) (SFe = 1/2) and Mn(iii) (SMn = 2) through cyanides and J2 between Mn(iii) ions via phenoxides, the best fits corresponded to J1 = 2.61 cm-1 and J2 = 0.85 cm-1 for 1, J1 = 2.50 cm-1 and J2 = 1.30 cm-1 for 2, and J 1 = -2.15 cm-1 and J2 = 0.55 cm-1 for 3. The phenoxide routes transmit ferromagnetic interactions in all cases, while ferromagnetic or antiferromagnetic couplings occur through the cyanide linkage. Although the geometric parameters relevant to the magnetic Fe-CN-Mn pathways are analogous to each other their magnetic natures are varied across the compounds, which supports that a degree of orbital overlap is quite sensitive to a subtle structural change in the present system.

AB - Three cyanide-linked Fe(iii)Mn(iii) bimetallic clusters, [(Tp)Fe(CN) 3]2[Mn(acphen)]2 [1; acphen = N,N′-ethylenebis(2-hydroxyacetophenylideneiminato) dianion], [(Tp)Fe(CN)3]2[Mn(5-Bracphen)]2 [2; 5-Bracphen = N,N′-ethylenebis(5-bromo-2-hydroxyacetophenylideneiminato) dianion], and [(Tp)Fe(CN)3]2[Mn(salen)]2·6H 2O [3; salen = N,N′-ethylenebis(salicylidineiminato) dianion], were prepared by self-assembling a facial [(Tp)Fe(CN)3]- [Tp = hydrotris(pyrazolyl)borate] precursor and respective Mn(iii) Schiff bases. X-Ray crystal structure analyses revealed that each complex is composed of a central Mn(iii) dimer doubly linked by phenoxides of the tetradentate N 2O2 Schiff bases and the terminal [(Tp)Fe(CN) 3]- groups connecting to the center through cyanides. Using the spin Hamiltonian H = -2J1(SFe1·S Mn1 + SMn1a·SFe1a) - 2J 2(SMn1·SMn1a), where J1 stands for the exchange coupling constant between Fe(iii) (SFe = 1/2) and Mn(iii) (SMn = 2) through cyanides and J2 between Mn(iii) ions via phenoxides, the best fits corresponded to J1 = 2.61 cm-1 and J2 = 0.85 cm-1 for 1, J1 = 2.50 cm-1 and J2 = 1.30 cm-1 for 2, and J 1 = -2.15 cm-1 and J2 = 0.55 cm-1 for 3. The phenoxide routes transmit ferromagnetic interactions in all cases, while ferromagnetic or antiferromagnetic couplings occur through the cyanide linkage. Although the geometric parameters relevant to the magnetic Fe-CN-Mn pathways are analogous to each other their magnetic natures are varied across the compounds, which supports that a degree of orbital overlap is quite sensitive to a subtle structural change in the present system.

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U2 - 10.1039/b818559j

DO - 10.1039/b818559j

M3 - Article

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AN - SCOPUS:61549120670

SN - 1477-9226

SP - 1954

EP - 1961

JO - Dalton Transactions

JF - Dalton Transactions

IS - 11

ER -

Syntheses, crystal structures and magnetic properties of cyano- and phenoxide-bridged Fe(iii)Mn(iii) tetramers containing fac-Fe(iii) tricyanides and Mn(iii) Schiff bases

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