Substituent effect on formation of heterometallic molecular wheels: Synthesis, crystal structure, and magnetic properties

Zhong Hai Ni, Li Fang Zhang, Vassilis Tangoulis, Wolfgang Wernsdorfer, Ai Li Cui, Osamu Sato, Hui Zhong Kou

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Abstract

The reaction of manganese(III) Schiff bases of the type salen2- (N,N′-ethylenebis(salicylideneaminato)) with X-substituted (X = CH 3, Cl) pyridinecarboxamide dicyanoferrite(III) [Fe(X-bpb)(CN) 2]- gave rise to a series of cyanide-bridged Mn 6Fe6 molecular wheels, [MnIII(salen)] 6[FeIII(bpmb)(CN)2]6·7H 2O (1), [Mn(salen)]6[Fe(bpClb)(CN)2] 6·4H2O·2CH3OH (2), [Mn(salen)]6[Fe(bpdmb)(CN)2]6·10H 2O·5CH3OH (3), [Mn(5-Br(salpn))] 6[Fe(bpmb)(CN)2]6·24H 2O·8CH3CN (4), and [Mn(5-Cl(salpn))] 6[Fe(bpmb)(CN)2]6·25H 2O·5CH3CN (5). Compared with [Fe(bpb)(CN) 2]-, which always gives rise to 1D or polynuclear species when reacting with Mn(III) Schiff bases, the introduction of substituents (X) to the bpb2- ligand has a driving force in formation of the novel wheel structure. Magnetic studies reveal that high-spin ground state S = 15 is present in the wheel compounds originated from the ferromagnetic Mn(III)-Fe(III) coupling. For the first time, the quantum Monte Carlo study has been used to modulate the magnetic susceptibility of the huge Mn6Fe6 metallomacrocycles, showing that the magnetic coupling constants J range from 3.0 to 8.0 K on the basis of the spin Hamiltonian H = J(Σ i,jsFeiSMnj + sFe1SMn12). Hysteresis loops for 1 have been observed below 0.8 K, indicative of a single-molecule magnet with a blocking temperature (TB) of 0.8 K. Molecular wheels 2-5 exhibit frequency dependence of alternating-current magnetic susceptibility under zero direct-current magnetic field, signifying the slow magnetization relaxation similar to that of 1. Significantly, an unprecedented archlike Mn2Fe2 cluster, [Mn(5-Cl(salpn))]2[Fe(bpmb)(CN)2]2· 3H2O·CH3CN (6), has been isolated as an intermediate of the Mn6Fe6 wheel 5. Ferromagnetic Mn(III)-Fe(III) coupling results in a high-spin S = 5 ground state. Combination of the high-spin state and a negative magnetic anisotropy (D) results in the observation of slow magnetization relaxation in 6.

Original languageEnglish
Pages (from-to)6029-6037
Number of pages9
JournalInorganic chemistry
Volume46
Issue number15
DOIs
Publication statusPublished - Jul 23 2007

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wheels
Magnetic properties
Wheels
Crystal structure
magnetic properties
crystal structure
synthesis
Schiff Bases
Magnetic susceptibility
Ground state
imines
Magnetization
magnetic permeability
Hamiltonians
Magnetic couplings
magnetization
ground state
Magnetic anisotropy
Cyanides
cyanides

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Substituent effect on formation of heterometallic molecular wheels : Synthesis, crystal structure, and magnetic properties. / Ni, Zhong Hai; Zhang, Li Fang; Tangoulis, Vassilis; Wernsdorfer, Wolfgang; Cui, Ai Li; Sato, Osamu; Kou, Hui Zhong.

In: Inorganic chemistry, Vol. 46, No. 15, 23.07.2007, p. 6029-6037.

Research output: Contribution to journalArticle

Ni, Zhong Hai ; Zhang, Li Fang ; Tangoulis, Vassilis ; Wernsdorfer, Wolfgang ; Cui, Ai Li ; Sato, Osamu ; Kou, Hui Zhong. / Substituent effect on formation of heterometallic molecular wheels : Synthesis, crystal structure, and magnetic properties. In: Inorganic chemistry. 2007 ; Vol. 46, No. 15. pp. 6029-6037.
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abstract = "The reaction of manganese(III) Schiff bases of the type salen2- (N,N′-ethylenebis(salicylideneaminato)) with X-substituted (X = CH 3, Cl) pyridinecarboxamide dicyanoferrite(III) [Fe(X-bpb)(CN) 2]- gave rise to a series of cyanide-bridged Mn 6Fe6 molecular wheels, [MnIII(salen)] 6[FeIII(bpmb)(CN)2]6·7H 2O (1), [Mn(salen)]6[Fe(bpClb)(CN)2] 6·4H2O·2CH3OH (2), [Mn(salen)]6[Fe(bpdmb)(CN)2]6·10H 2O·5CH3OH (3), [Mn(5-Br(salpn))] 6[Fe(bpmb)(CN)2]6·24H 2O·8CH3CN (4), and [Mn(5-Cl(salpn))] 6[Fe(bpmb)(CN)2]6·25H 2O·5CH3CN (5). Compared with [Fe(bpb)(CN) 2]-, which always gives rise to 1D or polynuclear species when reacting with Mn(III) Schiff bases, the introduction of substituents (X) to the bpb2- ligand has a driving force in formation of the novel wheel structure. Magnetic studies reveal that high-spin ground state S = 15 is present in the wheel compounds originated from the ferromagnetic Mn(III)-Fe(III) coupling. For the first time, the quantum Monte Carlo study has been used to modulate the magnetic susceptibility of the huge Mn6Fe6 metallomacrocycles, showing that the magnetic coupling constants J range from 3.0 to 8.0 K on the basis of the spin Hamiltonian H = J(Σ i,jsFeiSMnj + sFe1SMn12). Hysteresis loops for 1 have been observed below 0.8 K, indicative of a single-molecule magnet with a blocking temperature (TB) of 0.8 K. Molecular wheels 2-5 exhibit frequency dependence of alternating-current magnetic susceptibility under zero direct-current magnetic field, signifying the slow magnetization relaxation similar to that of 1. Significantly, an unprecedented archlike Mn2Fe2 cluster, [Mn(5-Cl(salpn))]2[Fe(bpmb)(CN)2]2· 3H2O·CH3CN (6), has been isolated as an intermediate of the Mn6Fe6 wheel 5. Ferromagnetic Mn(III)-Fe(III) coupling results in a high-spin S = 5 ground state. Combination of the high-spin state and a negative magnetic anisotropy (D) results in the observation of slow magnetization relaxation in 6.",
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T2 - Synthesis, crystal structure, and magnetic properties

AU - Ni, Zhong Hai

AU - Zhang, Li Fang

AU - Tangoulis, Vassilis

AU - Wernsdorfer, Wolfgang

AU - Cui, Ai Li

AU - Sato, Osamu

AU - Kou, Hui Zhong

PY - 2007/7/23

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N2 - The reaction of manganese(III) Schiff bases of the type salen2- (N,N′-ethylenebis(salicylideneaminato)) with X-substituted (X = CH 3, Cl) pyridinecarboxamide dicyanoferrite(III) [Fe(X-bpb)(CN) 2]- gave rise to a series of cyanide-bridged Mn 6Fe6 molecular wheels, [MnIII(salen)] 6[FeIII(bpmb)(CN)2]6·7H 2O (1), [Mn(salen)]6[Fe(bpClb)(CN)2] 6·4H2O·2CH3OH (2), [Mn(salen)]6[Fe(bpdmb)(CN)2]6·10H 2O·5CH3OH (3), [Mn(5-Br(salpn))] 6[Fe(bpmb)(CN)2]6·24H 2O·8CH3CN (4), and [Mn(5-Cl(salpn))] 6[Fe(bpmb)(CN)2]6·25H 2O·5CH3CN (5). Compared with [Fe(bpb)(CN) 2]-, which always gives rise to 1D or polynuclear species when reacting with Mn(III) Schiff bases, the introduction of substituents (X) to the bpb2- ligand has a driving force in formation of the novel wheel structure. Magnetic studies reveal that high-spin ground state S = 15 is present in the wheel compounds originated from the ferromagnetic Mn(III)-Fe(III) coupling. For the first time, the quantum Monte Carlo study has been used to modulate the magnetic susceptibility of the huge Mn6Fe6 metallomacrocycles, showing that the magnetic coupling constants J range from 3.0 to 8.0 K on the basis of the spin Hamiltonian H = J(Σ i,jsFeiSMnj + sFe1SMn12). Hysteresis loops for 1 have been observed below 0.8 K, indicative of a single-molecule magnet with a blocking temperature (TB) of 0.8 K. Molecular wheels 2-5 exhibit frequency dependence of alternating-current magnetic susceptibility under zero direct-current magnetic field, signifying the slow magnetization relaxation similar to that of 1. Significantly, an unprecedented archlike Mn2Fe2 cluster, [Mn(5-Cl(salpn))]2[Fe(bpmb)(CN)2]2· 3H2O·CH3CN (6), has been isolated as an intermediate of the Mn6Fe6 wheel 5. Ferromagnetic Mn(III)-Fe(III) coupling results in a high-spin S = 5 ground state. Combination of the high-spin state and a negative magnetic anisotropy (D) results in the observation of slow magnetization relaxation in 6.

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