Hierarchical Assembly of {Fe<sub>13</sub>} Oxygen‐Bridged Clusters into a Close‐Packed Superstructure

Murugesu, Muralee; Clérac, Rodolphe; Wernsdorfer, Wolfgang; Anson, Christopher E.; Powell, Annie K.

doi:10.1002/anie.200500208

Cited by 82 publications

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“…A comprehensive model description of 1 will also need to account for the various local ZFS effects by anisotropic exchange in a full spin Hamiltonian. Interestingly, nona-nuclear systems of the type [M 9 (OH) 3 (H 2 O) 6 2À anions-also feature similar ferromagnetic intratrimer and antiferromagnetic inter-trimer exchange. [20] Further experiments reflecting the local spin distribution of {Ni/ Co 12 } intermediates such as high-resolution ESR and MAS-1 H NMR spectroscopy are planned.…”

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confidence: 93%

“…a range of values for n) for a specified stoichiometric Ni:Co ratio. Using this relation, it is indeed possible to isolate all intermediates (n = 1-11) as pure compounds, two of which are reported herein: {Ni 11 Co 1 } (3) and {Ni 6 Co 6 } (4). Since classical analytical methods only can determine the bulk compositions of such compounds and single-crystal X-ray diffraction cannot unambiguously distinguish between single Ni and Co sites, probing the purity of 3 and 4, that is, the degree of compositional deviations from the stoichiometric Ni:Co average, had to rely primarily on physical-property arguments, differences in the crystal packing, and yield distributions.…”

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confidence: 96%

“…[6] In most instances the resulting metal frameworks are derived from various archetypal condensed substructures, such as (distorted) M 4 L 4 cubanes (M = metal, L = O, N, etc.). Such cubanes constitute a class of discrete compounds such as complexes based on Ni 4 O 4 or Co 4 O 4 structures, which themselves represent sections of their respective oxides.…”

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confidence: 99%

“…(1 a) and {Ni 12 } = [Ni 12 (trans-tachH) 6 (OMe) 12 (OAc) 9 (CO 3 )] 7+ (2 a) differ only in the relative amounts of m 3 -hydroxo and m 3 -methoxo groups found in the cubane units but show striking differences in the long-range ordering of clusters in the crystalline state; this is partly caused by the interactions between the protonated trans-amino groups in trans-tach between adjacent clusters in the crystal lattice. The cluster architectures are directed by the coordination of CO 3 2À ions and the formation of 1 and 2 is controlled by the availability of CO 3 2À ions.…”

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confidence: 99%

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Structural and Compositional Control in {M₁₂} Cobalt and Nickel Coordination Clusters Detected Magnetochemically and with Cryospray Mass Spectrometry

et al. 2007

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Full compositional and structural control in the high-nuclearity coordination clusters of transition-metal cations is a crucial synthetic target, and is motivated by these species complex electronic and magnetic properties which single them out as metalloenzyme models, [1] nanoscale containers and catalysts, [2] quantum computing components, [3] and molecular magnets.[4] Strategies for their synthesis range from the use of multifunctional organic ligands [5] to the controlled production of molecular sections of solid-state structures, such as those of transition-metal oxides.[6] In most instances the resulting metal frameworks are derived from various archetypal condensed substructures, such as (distorted) M 4 L 4 cubanes (M = metal, L = O, N, etc.). Such cubanes constitute a class of discrete compounds such as complexes based on Ni 4 O 4 or Co 4 O 4 structures, which themselves represent sections of their respective oxides. For the past four decades, these species have been studied as precursors for metal oxide nanoparticles, [7] novel magnetic materials, [8] and polymerization catalysts.[9] Coordination complexes of higher nuclearity, such as {Ni 11 }, [10] or {Co 14 } [11] frequently comprise corner-, edge-, or face-sharing aggregates of M II 4 O II 4 . As such, the generation of isostructural metalligand frameworks is especially important as they allow systematic, comparative studies of their complex magnetic phenomena and the possibility to precisely position heterometal atoms within a given architecture. However, while several almost isostructural compounds of Ni II and Co II exist, including M 4 O 4 cubane structures, because of their very similar coordination chemistry, [12] these are invariably of low nuclearity, and systems exceeding ten metal centers are rare.[13] Correspondingly, mixed-metal isostructures (i.e. structures incorporating both Ni II and Co II centers in varying ratios that are distributed over the metal framework of a coordination cluster) can be generated, yet site-specific occupation is frequently subject to binomial statistics and cannot be resolved by diffraction techniques. In such situations, as we demonstrate herein, magnetic properties can be used to discern between the possible intramolecular distribution scenarios and indicate how narrow the distribution curves are for (cocrystallizing) compositions (of the typeHerein, we demonstrate the use of templating and multifunctional ligands to facilitate the directed assembly of archetypal isostructural Ni [14]These clusters comprise three M 4 O 4 cubane units symmetrically arranged around a central templating carbonate anion and the intact clusters {M 12 } can be detected in solution using cryospray mass spectrometry.[15] Moreover, isostructural mixed Ni:Co clusters of specific composition can be accessed since the pH value of the reaction solution (i.e. an additional reaction parameter besides the stoichiometric reaction ratio of Ni and Co) is used to differentiate the relative population of the metal sites in the {M 12 } system. ...

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Structural and Compositional Control in {M₁₂} Cobalt and Nickel Coordination Clusters Detected Magnetochemically and with Cryospray Mass Spectrometry

et al. 2007

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Ein [Fe₁₉]‐“Super‐Lindqvist”‐Aggregat und ein großes, sich durchdringendes, dreidimensionales Koordinationspolymer aus Solvothermalreaktionen von [Fe₂(OtBu)₆] mit Ethanol

et al. 2015

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[2][3][4] 18, [5,6] 17, [7][8][9] 16, [10,11] 14 [12][13][14] und 13 [15,16] [24][25][26] Bisher wurde nur über sehr wenige molekulare Metall-Sauerstoff-Verbindungen mit mehr als drei m 6 -Oxo-Gruppen berichtet. [27][28][29][30] Ziel dieser Arbeit war die Synthese mehrkerniger EisenSauerstoff-Spezies mit mehr als zwei m 6 -Oxo-Gruppen. Zur Bildung hochaggregierter,k ugelfçrmiger Metall-SauerstoffVerbindungen schienen uns kleine organische Reste einfacher Alkoxo-Gruppen, wie Methoxo-oder Ethoxo-Gruppen, am ehesten geeignet. 24 ]( 1)k onnte durch Einkristallstrukturanalyse charakterisiert werden (Abbildungen 1u nd 2; Tabelle S1 der SI). [46] Komplex 1 enthält ausschließlich Fe III -Ionen. Da Va lenzsummenberechnungen (Tabellen S2 und S3 der SI) [33] sowie ATR-FT-IR-(Abbildungen S2-S6 der SI) und Mçßbauer-spektroskopische Untersuchungen (Abbildungen S7-S9 der SI) das Vorhandensein von Fe II -Ionen ausschließen, muss zum Ausgleichen der Ladungsbilanz eine Oxo-oder eine Ethoxo-Gruppe protoniert sein.[34] Diese Hypothese wird durch IR-spektroskopische Untersuchungen bestätigt, die darüber hinaus auf einen intramolekularen Protonentransfer zwischen den m 3 -Oxo-und den Ethoxo-Gruppen schließen

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Assembling Magnetic Nanowires into Networks: A Layered Co^IICarboxylate Coordination Polymer Exhibiting Single‐Chain‐Magnet Behavior

et al. 2006

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Chemists and physicists have jointly pushed the rapid progress of molecule-based nanomagnets in recent years. [1] Since the first discovery of single-molecule magnets (SMMs) in the 1990s, [2] exciting discoveries in this area have included single-chain magnets (SCMs, or so-called magnetic nanowires) [3] and a hydrogen-bonded SMM dimer, [4] which can be regarded as expansions of SMMs by intermolecular magnetic interactions. [4, 5] These observations have encouraged chemists to construct or tailor SMMs into an extended network with the hope that certain cooperative effects mediated by covalent linkers could improve the quantum properties of the original units. [5][6][7] This idea has led to a variety of interesting SMM networks exhibiting properties from classical to quantum magnetism [6,7] and provided useful subjects for studying the effects of intermolecular interactions on the behavior arising from the energy barrier to magnetization reversal. [4][5][6][7] In contrast to the rapid development of SMM networks, SCM networks are significantly restricted, which may be attributable to the difficulty in arranging these magnetic nanowires while maintaining a sufficiently large ratio of intra-to interchain magnetic interaction to "freeze in" one-dimensional (1D) magnetization and prevent 3D ordering.[3] Thus, it is important to use proper covalent linkers, which should have at least two features: 1) multitopic structure to covalently link the chains; 2) magnetically "inertness" to efficiently prevent magnetic interactions between the chains.As s-bonding linkers are significantly weaker mediators of the spin carriers, [8] crystal engineering with a judicious choice of s-bonding ditopic linkers may allow us to covalently link 1D Ising ferro-or ferrimagnetic chains into 2D or 3D networks without significant deterioration of the one-dimensional magnetism of the SCMs in the 2D or 3D structures, although no genuine example has been reported so far. In this regard, trans-1,2-cyclohexanedicarboxylate (trans-1,2-chdc) is a good candidate, since it was demonstrated to be a very weak magnetic mediator [9] due to alternation effects.[8]As part of our ongoing search for new magnetic coordination polymers, [10] we chose this ligand as a structural linker and magnetic separator to incorporate magnetic anisotropic chains into a higher dimensional network. We have used trans-1,2-chdc to prepare laminated coordination polymer 2 1 [Co II 3 (OH) 2 (trans-1,2-chdc) 2 ] (1) exhibiting magnetism due to coexistent spin frustration and long-range magnetic ordering.[10a] Interestingly, at lower reaction pH value and temperature, we obtained the new laminated product 2 1 [Co II (trans-1,2-chdc)] (2) as a pure phase, which consists of a parallel arrangement of carboxylate-bridged, paddle-wheel Co II chains and shows interesting SCM behavior.In the single-crystal structure of 2, the Co II atom (Figure 1 and Figure S1) adopts a slightly distorted square-pyramidal geometry with four basal oxygen atoms (CoÀO 1.971(3)-2.210(3) ) and one apical oxy...

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Hierarchical Assembly of {Fe₁₃} Oxygen‐Bridged Clusters into a Close‐Packed Superstructure

Cited by 82 publications

References 27 publications

Structural and Compositional Control in {M₁₂} Cobalt and Nickel Coordination Clusters Detected Magnetochemically and with Cryospray Mass Spectrometry

Structural and Compositional Control in {M₁₂} Cobalt and Nickel Coordination Clusters Detected Magnetochemically and with Cryospray Mass Spectrometry

Ein [Fe₁₉]‐“Super‐Lindqvist”‐Aggregat und ein großes, sich durchdringendes, dreidimensionales Koordinationspolymer aus Solvothermalreaktionen von [Fe₂(OtBu)₆] mit Ethanol

Assembling Magnetic Nanowires into Networks: A Layered Co^IICarboxylate Coordination Polymer Exhibiting Single‐Chain‐Magnet Behavior

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Hierarchical Assembly of {Fe13} Oxygen‐Bridged Clusters into a Close‐Packed Superstructure

Cited by 82 publications

References 27 publications

Structural and Compositional Control in {M12} Cobalt and Nickel Coordination Clusters Detected Magnetochemically and with Cryospray Mass Spectrometry

Structural and Compositional Control in {M12} Cobalt and Nickel Coordination Clusters Detected Magnetochemically and with Cryospray Mass Spectrometry

Ein [Fe19]‐“Super‐Lindqvist”‐Aggregat und ein großes, sich durchdringendes, dreidimensionales Koordinationspolymer aus Solvothermalreaktionen von [Fe2(OtBu)6] mit Ethanol

Assembling Magnetic Nanowires into Networks: A Layered CoIICarboxylate Coordination Polymer Exhibiting Single‐Chain‐Magnet Behavior

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Hierarchical Assembly of {Fe₁₃} Oxygen‐Bridged Clusters into a Close‐Packed Superstructure

Structural and Compositional Control in {M₁₂} Cobalt and Nickel Coordination Clusters Detected Magnetochemically and with Cryospray Mass Spectrometry

Structural and Compositional Control in {M₁₂} Cobalt and Nickel Coordination Clusters Detected Magnetochemically and with Cryospray Mass Spectrometry

Ein [Fe₁₉]‐“Super‐Lindqvist”‐Aggregat und ein großes, sich durchdringendes, dreidimensionales Koordinationspolymer aus Solvothermalreaktionen von [Fe₂(OtBu)₆] mit Ethanol

Assembling Magnetic Nanowires into Networks: A Layered Co^IICarboxylate Coordination Polymer Exhibiting Single‐Chain‐Magnet Behavior