Solvothermal Synthesis of a Tetradecametallic Fe<sup>III</sup> Cluster

Low, David M.; Jones, Leigh F.; Bell, Aidan; Brechin, Euan K.; Mallah, Talal; Rivière, Éric; Teat, Simon J.; McInnes, Eric J. L.

doi:10.1002/anie.200351865

Cited by 134 publications

(62 citation statements)

References 29 publications

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“…We recently reported the solvothermal synthesis of highnuclearity Cr III [8] and Fe III [9] species via simple trimetallic ™basic metal carboxylates∫-[M 3 O(O 2 CR) 6 L 3 ]X (R = alkyl, aryl; L = for example, pyridine (py), H 2 O; X = anion)-in superheated alcoholic solutions. We reasoned that this route should also be amenable to V III clusters because the vanadium trimers are known [10] and the reducing nature of alcohols under solvothermal conditions should prevent oxidation of [ [11] but not discrete clusters.…”

Section: Introductionmentioning

confidence: 99%

Solvothermal Syntheses of High‐Nuclearity Vanadium(III) Clusters

Laye

Murrie

Ochsenbein

et al. 2003

Chemistry A European J

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Superheating alcohol solutions of simple trimetallic vanadium(III) precursors gives the octa- and decametallic vanadium(III) clusters [V(8)(OEt)(8)(OH)(4)(O(2)CPh)(12)] (1) and [V(10)(OMe)(20)(O(2)CMe)(10)] (2). Cluster 2 is the largest vanadium(III) cluster synthesised to date. Thus solvothermal synthetic techniques are an excellent route to high-nuclearity vanadium(III) clusters. Both 1 and 2 consist of a planar or near-planar array of V(III) ions. The metal ions in 1 are bridged by either a micro(2)-hydroxide and two micro(2)-benzoate groups or two micro(2)-ethoxides and a micro(2)-benzoate groups, the two bridging arrangements alternating around the ring. In 2 each pair of neighbouring metal ions is bridged by two micro(2)-methoxides and a micro(2)-acetate, and this molecule is the V(III) analogue of Lippard's famous "ferric wheel". Preliminary magnetic susceptibility studies show the exchange coupling in both complexes to be antiferromagnetic in nature, with the coupling stronger in 1 than in 2.

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Section: Introductionmentioning

confidence: 99%

Solvothermal Syntheses of High‐Nuclearity Vanadium(III) Clusters

Laye

Murrie

Ochsenbein

et al. 2003

Chemistry A European J

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“…[5] One consequence of this phenomenon is the possibility of using single molecules as information-storage devices. The last ten years has seen many attempts to produce new SMMs in the same mould as the original SMM [Mn 12 O 12 (OAc) 16 (H 2 O) 4 ]·4 H 2 O·2 CH 3 CO 2 H, [6] and this has led to the discovery of numerous SMMs ranging in nuclearity from 4 to 84. [7] The majority of SMMs reported to date have been clusters that contain Mn III ions.…”

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confidence: 99%

“…Benzotriazole has previously been used to produce model compounds for corrosion inhibition studies [10] and in M II cluster chemistry; [11] however, until recently, it has never been used in the synthesis of M III clusters. [12] Metal fluorides have been used to good effect in the synthesis of polymetallic chromium carboxylates [13] and, to a lesser extent, of Fe III clusters, including the synthesis of an open-shell Keggin iron ion, [14] but have thus far rarely been used in manganese cluster chemistry. [15] The main disadvantage of the use of metal fluorides is their relative insolubility and therefore the apparent need for more "complicated" synthetic procedures.…”

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confidence: 99%

New Routes to Polymetallic Clusters: Fluoride‐Based Tri‐, Deca‐, and Hexaicosametallic Mn^III Clusters and their Magnetic Properties

Jones

Rajaraman

Brockman

et al. 2004

Chemistry A European J

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The syntheses, structures and magnetic properties of three new MnIII clusters, [Mn26O17(OH)8(OMe)4F10(bta)22(MeOH)14(H2O)2] (1), [Mn(0O6(OH)2(bta)8(py)8F8] (2) and [NHEt3]2[Mn3O(bta)6F3] (3), are reported (bta=anion of benzotriazole), thereby demonstrating the utility of MnF3 as a new synthon in Mn cluster chemistry. The "melt" reaction (100 degrees C) between MnF(3) and benzotriazole (btaH, C6H5N3) under an inert atmosphere, followed by dissolution in MeOH produces the cluster [Mn26O17(OH)8(OMe)4F10(bta)22(MeOH)14(H2O)2] (1) after two weeks. Complex 1 crystallizes in the triclinic space group P1, and consists of a complicated array of metal tetrahedra linked by mu3-O2- ions, mu3- and mu2-OH- ions, mu2-MeO- ions and mu2-bta- ligands. The "simpler" reaction between MnF3 and btaH in boiling MeOH (50 degrees C) also produces complex 1. If this reaction is repeated in the presence of pyridine, the decametallic complex [Mn10O6(OH)2(bta)8(py)8F8] (2) is produced. Complex 2 crystallizes in the triclinic space group P1 and consists of a "supertetrahedral" [Mn(III)10] core bridged by six mu3-O2- ions, two mu3-OH- ions, four mu2-F- ions and eight mu2-bta- ions. The replacement of pyridine by triethylamine in the same reaction scheme produces the trimetallic species [NHEt3]2[Mn3O(bta)6F3] (3). Complex 3 crystallises in the monoclinic space group P2(1)/c and has a structure analogous to that of the basic metal carboxylates of general formula [M3O(RCO2)6L3]0/+, which consists of an oxo-centred metal triangle with mu2-bta- ligands bridging each edge of the triangle and the fluoride ions acting as the terminal ligands. DC magnetic susceptibility measurements in the 300-1.8 K and 0.1-7 T ranges were investigated for all three complexes. For each, the value of chi(M)T decreases with decreasing temperatures; this indicates the presence of dominant antiferromagnetic exchange interactions in 1-3. For complex 1, the low-temperature value of chi(M)T is 10 cm(3) K mol(-1) and fitting of the magnetisation data gives S=4, g=2.0 and D=-0.90 cm(-1). For complex 2, the value of chi(M)T falls to a value of approximately 5.0 cm(3) K mol(-1) at 1.8 K, which is consistent with a small spin ground state. For the triangular complex 3, the best fit to the experimental chi(M)T versus T data was obtained for the following parameters: Ja = -5.01 cm(-1), Jb = +9.16 cm(-1) and g=2.00, resulting in an S=2 spin ground state. DFT calculations on 3, however, suggest an S=1 or S=0 ground state with J(a)=-2.95 cm(-1) and J(b)=-2.12 cm(-1). AC susceptibility measurements performed on 1 in the 1.8-4.00 K range show the presence of out-of-phase AC susceptibility signals, but no peaks. Low-temperature single-crystal studies performed on 1 on an array of micro-SQUIDS show the time- and temperature-dependent hysteresis loops indicative of single-molecule magnetism behaviour.

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“…15,16 We have explored hydro(solvo)thermal techniques by introducing the strategy to the synthesis of metallaborane to obtain two (8) 3053 (1) 7047 (1) 1349 (1) 22 (1) C (20) 1940 (7) 11 067 (7) 1322 (5) 47(3) B (1) 3425 (7) 7375 (7) 2727 (4) 28 (3) C (21) 2177 (8) 11 609 (8) 895 (7) 72(4) B (2) 2638 (7) 8218 (7) 2570 (4) 26 (3) C (22) 1902 (10) 11 438 (10) 371 (6) 71(4) B (3) 3455 (8) 7886 (8) 2096 (4) 33 (3) C (23) 1397 (9) 10 730 (9) 240 (5) 61(4) B (4) 3649 (7) 6686 (7) 2189 (4) 25 (3) C (24) 1172 (7) 10 195 (7) 642 (5) 46(3) B (5) 2920 (8) 6329 (8) 2662 (5) 30 (3) C (25) 35 (6) 9350 (7) 1483 …”

Section: Synthesis and Characterizationunclassified

Synthesis and crystal structure of three nido 11‐vertex platinaborane clusters

Dou¹,

Wu²,

Guo³

et al. 2005

Applied Organom Chemis

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Solvothermal Synthesis of a Tetradecametallic Fe^III Cluster

Cited by 134 publications

References 29 publications

Solvothermal Syntheses of High‐Nuclearity Vanadium(III) Clusters

Solvothermal Syntheses of High‐Nuclearity Vanadium(III) Clusters

New Routes to Polymetallic Clusters: Fluoride‐Based Tri‐, Deca‐, and Hexaicosametallic Mn^III Clusters and their Magnetic Properties

Synthesis and crystal structure of three nido 11‐vertex platinaborane clusters

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Solvothermal Synthesis of a Tetradecametallic FeIII Cluster

Cited by 134 publications

References 29 publications

Solvothermal Syntheses of High‐Nuclearity Vanadium(III) Clusters

Solvothermal Syntheses of High‐Nuclearity Vanadium(III) Clusters

New Routes to Polymetallic Clusters: Fluoride‐Based Tri‐, Deca‐, and Hexaicosametallic MnIII Clusters and their Magnetic Properties

Synthesis and crystal structure of three nido 11‐vertex platinaborane clusters

Contact Info

Product

Resources

About

Solvothermal Synthesis of a Tetradecametallic Fe^III Cluster

New Routes to Polymetallic Clusters: Fluoride‐Based Tri‐, Deca‐, and Hexaicosametallic Mn^III Clusters and their Magnetic Properties