Magnetic exchange interactions in the linear-chain chromium(III) compounds

Schwartz, Michael A.; Hatfield, William E.; Joesten, Melvin D.; Hanack, Michael; Datz, A.

doi:10.1021/ic00218a043

Cited by 30 publications

(5 citation statements)

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“…The delta d xy −d xy interaction is much more reduced in magnitude and then a global ferromagnetic interaction is observed. Noteworthy, a similar unexpected ferromagnetic coupling has been also observed between Cr(t 2g 3) ions in the compound catena-cyano(phthalocyaninato) chromium(III) …”

Section: Resultssupporting

confidence: 65%

Cyano-Bridged Bimetallic Assemblies from Hexacyanometalate, [M(CN)₆]^3-(M = Mn^IIIand Fe^III), and [M(N₄-macrocycle)]²⁺(M = Fe^III, Ni^IIand Zn^II) Building Blocks. Syntheses, Multidimensional Structures, and Magnetic Properties

et al. 2001

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Reactions between [M(N(4)-macrocycle)](2+) (M = Zn(II) and Ni(II); macrocycle ligands are either CTH = d,l-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane or cyclam = 1,4, 8, 11-tetrazaazaciclotetradecane) and [M(CN)(6)](3-) (M = Fe(III) and Mn(III)) give rise to cyano-bridged assemblies with 1D linear chain and 2D honeycomblike structures. The magnetic measurements on the 1D linear chain complex [Fe(cyclam)][Fe(CN)(6)].6H(2)O 1 points out its metamagnetic behavior, where the ferromagnetic interaction operates within the chain and the antiferromagnetic one between chains. The Neel temperature, T(N), is 5.5 K and the critical field at 2 K is 1 T. The unexpected ferromagnetic intrachain interaction can be rationalized on the basis of the axially elongated octahedral geometry of the low spin Fe(III) ion of the [Fe(cyclam)](3+) unit. The isostructural substitution of [Fe(CN)(6)](3-) by [Mn(CN)(6)](3-) in the previously reported complex [Ni(cyclam)](3)[Fe(CN)(6)](2).12H(2)O 2 leads to [Ni(cyclam)](3)[Mn(CN)(6)](2).16 H(2)O 3, which exhibits a corrugated 2D honeycomblike structure and a metamagnetic behavior with T(N) = 16 K and a critical field of 1 T. In the ferromagnetic phase (H > 1 T) this compound shows a very important coercitive field of 2900 G at 2 K. Compound [Ni(CTH)](3)[Fe(CN)(6)](2).13H(2)O 4, C(60)H(116)Fe(2)N(24)Ni(3)O(13), monoclinic, A 2/n, a = 20.462(7), b = 16.292(4), c = 27.262(7) A, beta = 101.29(4) degrees, Z = 4, also has a corrugated 2D honeycomblike structure and a ferromagnetic intralayer interaction, but, in contrast to 2 and 3, does not exhibit any magnetic ordering. This fact is likely due to the increase of the interlayer separation in this compound. ([Zn(cyclam)Fe(CN)(6)Zn(cyclam)] [Zn(cyclam)Fe(CN)(6)].22H(2)O.EtOH) 5, C(44)H(122)Fe(2)N(24)O(23)Zn(3), monoclinic, A 2/n, a = 14.5474(11), b = 37.056(2), c = 14.7173(13) A, beta = 93.94(1) degrees, Z = 4, presents an unique structure made of anionic linear chains containing alternating [Zn(cyclam)](2+) and [Fe(CN)(6)](3)(-) units and cationic trinuclear units [Zn(cyclam)Fe(CN)(6)Zn(cyclam)](+). Their magnetic properties agree well with those expected for two [Fe(CN)(6)](3-) units with spin-orbit coupling effect of the low spin iron(III) ions.

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Section: Resultssupporting

confidence: 65%

Cyano-Bridged Bimetallic Assemblies from Hexacyanometalate, [M(CN)₆]^3-(M = Mn^IIIand Fe^III), and [M(N₄-macrocycle)]²⁺(M = Fe^III, Ni^IIand Zn^II) Building Blocks. Syntheses, Multidimensional Structures, and Magnetic Properties

et al. 2001

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“…In our case the geometry of the M-C-N-M units is less regular, with one of the metals, Mn, in a six coordinate bipyramidal coordination and the C-N-Mn angle different from 180°, at least for the pentamer and the intertrimer interactions. We also recall that an unexpected antiferromagnetic coupling has been observed between two CN - bridged bipyramidal Cr(III) [ d 3 , ( t 2g ) 3 ], in the catena -cyano(phthalocyaninato)chromium(III) …”

Section: Resultsmentioning

confidence: 83%

“…Magnetostructural Correlation. The magnetic interaction between various combinations of two magnetic centers A and B with a CN - group has been examined experimentally and theoretically …”

Section: Resultsmentioning

confidence: 99%

Complexes Derived from the Reaction of Manganese(III) Schiff Base Complexes and Hexacyanoferrate(III): Syntheses, Multidimensional Network Structures, and Magnetic Properties

et al. 1996

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The reaction between the [Mn(BS)(H2O)]+ monomeric and [Mn2(μ-BS)2(H2O)2]2+ dimeric cations and [Fe(CN)6]3- gave rise to cation−anion interaction via the formation of [FeC⋮NMn] bridges. Depending on the nature of the Schiff base and regardless of the stoichiometry used, either the trimeric anion [{Mn(BS)}2{Fe(CN)6}]- (BS = 3-MeOsalen, 6; 5-Clsalen, 7; 5-Brsalen, 8; salcy, 10) or the pentameric cation [{Mn(BS)}4{Fe(CN)6}]+ (BS = saltmen, 9) is formed, which has been assembled by the K+ cation or the ClO4 - anion, respectively. The X-ray analysis of 6 revealed a two-dimensional network layer structure. The magnetic measurements showed its metamagnetic behavior, where the ferromagnetic interaction operates within each layer and the antiferromagnetic interaction operates between the layers. The Neel temperature, T N, is 9.2 K, and the critical field at 2 K is 300 Oe. The temperature dependent magnetic susceptibilities of 7 and 8 are in agreement with a discrete, symmetrical, trinuclear structure Mn(III)Fe(III)Mn(III) (S Mn = 2, S Fe = 1/2, S Mn = 2) with a ferromagnetic spin coupling between the Mn(III) and Fe(III) ions, a small antiferromagnetic intertrimer interaction, and a large zero-field splitting of the Mn(III) ion. The structure of 9 consists of a two-dimensional layer containing as the repeating unit a cyclic dodecamer. The layers stack along the c axis, and ClO4 - anions are positioned between the layers. The magnetic measurements showed this compound's ferromagnetic behavior. There are, in fact, two kinds of intralayer magnetic interactions, the interaction between the Fe(III) and Mn(III) ions bridged by CN groups and the interaction between two Mn(III) ions in the dimer [Mn2(saltmen)2], both being ferromagnetic. The interlayer magnetic interaction is ferromagnetic. All of the interactions render to 9 an overall ferromagnetic behavior.

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“…Dependence of the First-Order Rate Constant (Aobsd) on pH for the Oxidation of the pida Complex0 of m-Aquaoxovanadium(IV) (0.0094 M) with [IrCl6]2" (1.99 X 10"4 M) at / = 0.1 M (NaC104) and 25 °C pH °pida4" = ((phosphonomethyl)imino)diacetate(4-). 4 Each value is an average of at least three kinetic runs. (-) or LiC104 (---) for the oxidation of [VO(pida)(H20)]2" (2.00 X 10"3 M) with [IrCl6]2" (2.75 X 10"5 M) at pH 5.7 ± 0.2 at 25 °C.…”

Section: Resultsmentioning

confidence: 99%

Kinetics of ligand substitution and oxidation reactions of the [((phosphonomethyl)imino)diacetato]aquaoxovanadium(IV) ion: role of the hydrogen bond between the coordinated water and the phosphonate arm

Wang¹,

Sasaki²,

Okazaki³

et al. 1986

Inorg. Chem.

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Magnetic exchange interactions in the linear-chain chromium(III) compounds

Cited by 30 publications

References 0 publications

Cyano-Bridged Bimetallic Assemblies from Hexacyanometalate, [M(CN)₆]^3-(M = Mn^IIIand Fe^III), and [M(N₄-macrocycle)]²⁺(M = Fe^III, Ni^IIand Zn^II) Building Blocks. Syntheses, Multidimensional Structures, and Magnetic Properties

Cyano-Bridged Bimetallic Assemblies from Hexacyanometalate, [M(CN)₆]^3-(M = Mn^IIIand Fe^III), and [M(N₄-macrocycle)]²⁺(M = Fe^III, Ni^IIand Zn^II) Building Blocks. Syntheses, Multidimensional Structures, and Magnetic Properties

Complexes Derived from the Reaction of Manganese(III) Schiff Base Complexes and Hexacyanoferrate(III): Syntheses, Multidimensional Network Structures, and Magnetic Properties

Kinetics of ligand substitution and oxidation reactions of the [((phosphonomethyl)imino)diacetato]aquaoxovanadium(IV) ion: role of the hydrogen bond between the coordinated water and the phosphonate arm

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Magnetic exchange interactions in the linear-chain chromium(III) compounds

Cited by 30 publications

References 0 publications

Cyano-Bridged Bimetallic Assemblies from Hexacyanometalate, [M(CN)6]3-(M = MnIIIand FeIII), and [M(N4-macrocycle)]2+(M = FeIII, NiIIand ZnII) Building Blocks. Syntheses, Multidimensional Structures, and Magnetic Properties

Cyano-Bridged Bimetallic Assemblies from Hexacyanometalate, [M(CN)6]3-(M = MnIIIand FeIII), and [M(N4-macrocycle)]2+(M = FeIII, NiIIand ZnII) Building Blocks. Syntheses, Multidimensional Structures, and Magnetic Properties

Complexes Derived from the Reaction of Manganese(III) Schiff Base Complexes and Hexacyanoferrate(III): Syntheses, Multidimensional Network Structures, and Magnetic Properties

Kinetics of ligand substitution and oxidation reactions of the [((phosphonomethyl)imino)diacetato]aquaoxovanadium(IV) ion: role of the hydrogen bond between the coordinated water and the phosphonate arm

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Cyano-Bridged Bimetallic Assemblies from Hexacyanometalate, [M(CN)₆]^3-(M = Mn^IIIand Fe^III), and [M(N₄-macrocycle)]²⁺(M = Fe^III, Ni^IIand Zn^II) Building Blocks. Syntheses, Multidimensional Structures, and Magnetic Properties

Cyano-Bridged Bimetallic Assemblies from Hexacyanometalate, [M(CN)₆]^3-(M = Mn^IIIand Fe^III), and [M(N₄-macrocycle)]²⁺(M = Fe^III, Ni^IIand Zn^II) Building Blocks. Syntheses, Multidimensional Structures, and Magnetic Properties