Synthesis and characterization of the first main group oxo-centered trinuclear carboxylate

Andras, Maria T.; Duraj, Stan A.; Hepp, Aloysius F.; Fanwick, Phillip E.; Bodnar, Matthew M.

doi:10.1021/ja00028a070

Cited by 28 publications

(14 citation statements)

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“…To our knowledge, the six‐membered cyclic structure of 2 is unprecedented among oxo‐bridged gallium( III ) clusters. These include the trimeric μ 3 ‐oxo‐centered carboxylate [Ga 3 (O)(O 2 CPh) 6 (4‐Me‐py) 3 ] + ,19a the tetranuclear complex [Ga 4 (OH) 6 (3‐ t Bu‐Hpz) 10 ] 6+ with a “butterfly” core,19b and the octagallium( III ) cluster [Ga 8 (pz) 12 O 4 Cl 4 ] (Hpz=pyrazole) 20. In the latter, four penta‐coordinated gallium( III ) ions are connected to an inner Ga 4 O 4 cubane core through μ 4 ‐oxo and pyrazolato bridges.…”

Section: Resultsmentioning

confidence: 99%

Single-Ion versus Dipolar Origin of the Magnetic Anisotropy in Iron(III)-Oxo Clusters: A Case Study

et al. 2001

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A multitechnique approach has allowed the first experimental determination of single-ion anisotropies in a large iron(III)-oxo cluster, namely [NaFe6(OCH3)12(pmdbm)6ClO4 (1) in which Hpmdbm = 1,3-bis(4-methoxyphenyl)-1,3-propanedione. High-frequency EPR (HF-EPR). bulk susceptibility measurements, and high-field cantilever torque magnetometry (HF-CTM) have been applied to iron-doped samples of an isomorphous hexagallium(III) cluster [NaGa6(OCH3)12-(pmdbm)6]ClO4, whose synthesis and X-ray structure are also presented. HF-EPR at 240 GHz and susceptibility data have shown that the iron(III) ions have a hard-axis type anisotropy with DFe = 0.43(1) cm(-1) and EFe = 0.066(3) cm(-1) in the zero-field splitting (ZFS) Hamiltonian H = DFe[S2(z) - S(S + 1)/3] + Fe[S2(x) - S2(y)]. HF-CTM at 0.4 K has then been used to establish the orientation of the ZFS tensors with respect to the unique molecular axis of the cluster, Z. The hard magnetic axes of the iron(III) ions are found to be almost perpendicular to Z, so that the anisotropic components projected onto Z are negative, DFe(ZZ)= -0.164(4) cm(-1). Due to the dominant antiferromagnetic coupling, a negative DFe(ZZ) value determines a hard-axis molecular anisotropy in 1, as experimentally observed. By adding point-dipolar interactions between iron(III) spins, the calculated ZFS parameter of the triplet state, D1 = 4.70(9) cm(-1), is in excellent agreement with that determined by inelastic neutron scattering experiments at 2 K, D1 = 4.57(2) cm(-1). Iron-doped samples of a structurally related compound, the dimer [Ga2(OCH3)2(dbm)4] (Hdbm = dibenzoylmethane), have also been investigated by HF-EPR at 525 GHz. The single-ion anisotropy is of the hard-axis type as well, but the DFe parameter is significantly larger [DFe = 0.770(3) cm(-1). EFe = 0.090(3) cm(-1)]. We conclude that, although the ZFS tensors depend very unpredictably on the coordination environment of the metal ions, single-ion terms can contribute significantly to the magnetic anisotropy of iron(III)-oxo clusters, which are currently investigated as single-molecule magnets.

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Section: Resultsmentioning

confidence: 99%

Single-Ion versus Dipolar Origin of the Magnetic Anisotropy in Iron(III)-Oxo Clusters: A Case Study

et al. 2001

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“…However, the two coordination spheres are different in two respects. [For the compound prepared by Andras et al (1992), the only previous example to exhibit such a bridge, the bridging Ga--O distances were, however, the shortest of the gallium coordination.] Secondly, the relative arrangements of the ligands are different.…”

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confidence: 99%

A Phenoxo-Bridged Digallium(III) Complex with a Ligand Derived from 2,6-Bis{[N,N'-bis(carboxymethyl)amino]methyl}-4-methylphenol

Jarjayes¹,

d′Hardemare²,

Durif³

et al. 1998

Acta Crystallogr C

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“…The solid state structure of 5 reveals a discrete ion pair formed by the cationic bis-chelate species [Ga{N-(SP i Pr 2 )(SeP i Pr 2 )-S, Se} 2 ] + containing a tetracoordinated Ga(III) center surrounded by four chalcogen donor atoms in a tetrahedral environment and the [GaCl 4 ] À anion. The central Ga(2) atom in the [GaCl 4 ] À anion has a distorted tetrahedral coordination sphere with common features to similar anions [9,10]. The chlorine atoms are disordered over two positions and due to the high symmetry of the molecule, the sulfur and selenium atoms are sharing the same position with an occupancy factor of 0.5 (Fig.…”

Section: Gallium Complexesmentioning

confidence: 94%

Synthesis and structural characterization of gallium and indium complexes obtained from redistribution reactions of mixed chalcogen-imidodiphosphinate ligands

Moya‐Cabrera

Cea‐Olivares

Alcántara-García

et al. 2005

Journal of Organometallic Chemistry

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Synthesis and characterization of the first main group oxo-centered trinuclear carboxylate

Cited by 28 publications

References 1 publication

Single-Ion versus Dipolar Origin of the Magnetic Anisotropy in Iron(III)-Oxo Clusters: A Case Study

Single-Ion versus Dipolar Origin of the Magnetic Anisotropy in Iron(III)-Oxo Clusters: A Case Study

A Phenoxo-Bridged Digallium(III) Complex with a Ligand Derived from 2,6-Bis{[N,N'-bis(carboxymethyl)amino]methyl}-4-methylphenol

Synthesis and structural characterization of gallium and indium complexes obtained from redistribution reactions of mixed chalcogen-imidodiphosphinate ligands

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