Supramolekulare Anorganische Chemie: von Gästen in kleinen und großen Wirten

Müller, Achim; Reuter, Hans; Dillinger, Stephan

doi:10.1002/ange.19951072104

Cited by 136 publications

(41 citation statements)

References 213 publications

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“…[22] In these reactions anions control the aggregation of V (15), in which the anions are encapsulated inside the cavity of these spherical clusters. With other anions such as acetate, VÀO aggregates are formed in which the anions are located on the outer surface of the shell.…”

Section: Linear and Trigonal-planar Anionsmentioning

confidence: 99%

Anion‐Templated Synthesis

2003

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In contrast to the well-studied templating properties of cationic and neutral species there are relatively few examples of anion-templated syntheses. This is attributed to some of the intrinsic properties of anions such as their diffuse nature, pH sensitivity, and their relative high solvation free energies. However, the increasing number of anion-templated assemblies reported over the past few years demonstrates that these limitations are not as critical as first thought. This review summarizes the most important results on the use of anions as directing agents for the syntheses of a wide range of inorganic and organic assemblies (such as macrocycles, cages, helicates, rotaxanes, and extended structures). It is hoped that this will stimulate a closer look into this emerging area of supramolecular chemistry.

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Section: Linear and Trigonal-planar Anionsmentioning

confidence: 99%

Anion‐Templated Synthesis

2003

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“…This phenomenon is especially prevalent in polyoxometallate chemistry, where there are direct bonds between the encapsulated guest, which is usually an oxoanion, and metal ions in the metallate cage. [1] However, there are also an increasing number of polynuclear coordination compounds, with two-or three-dimensional cage structures surrounding a guest species. [2] In these latter compounds there are often no covalent bonds between the guest and the complex host; instead, the guest interacts with the cage only by electrostatics, hydrogen-bonding, or other secondary interactions.…”

Section: Introductionmentioning

confidence: 99%

Reactions of Copper(II) Salts with 3{5}‐tert‐Butylpyrazole: Double‐Cubane Complexes with Bound Exogenous Anions, and a Novel Pyrazole Coordination Mode

Liu

McAllister

Miranda

et al. 2004

Chemistry A European J

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Reaction of CuX(2) (X(-)=Cl(-), Br(-), NO(3) (-)), NaOH, and 3[5]-tert-butylpyrazole (Hpz(tBu)) in a 1:1:2 molar ratio in MeOH at 293 K for three days affords [[Cu(3)(Hpz(tBu))(6)(mu(3)-X)(mu(3)-OH)(3)](2)Cu]X(6) (X(-)=Cl(-), 1; X(-)=Br(-), 2; X(-)=NO(3)(-), 3) in moderate yields. These compounds contain a centrosymmetric, vertex-sharing double-cubane [[Cu(3)(Hpz(tBu))(6)(mu(3)-X)(mu(3)-OH)(3)](2)Cu](6+) core, surrounded by a belt of six hydrogen-bonded X(-) ions. For 1 and 2, the ring of guest anions has near C(3) symmetry, that is slightly distorted owing to the axis of Jahn-Teller elongation at the central Cu ion. For 3 only, the NO(3)(-) guest ions are crystallographically disordered, reflecting their poor complimentarity with complex host. A similar reaction employing CuF(2) yields [[Cu(3)(Hpz(tBu))(4)(mu-pz(tBu))(2)(mu-F)(2)(mu(3)-F)](2)]F(2) (4), whose structure contains a cyclic hexacopper core with approximate C(2v) symmetry. Finally, an analogous reaction using Cu(NCS)(2) gives a mixture of trans-[Cu(NCS)(2)(Hpz(tBu))(2)] (5) and [Cu(2)(NCS)(2)(mu-pz(tBu))(2)(mu-Hpz(tBu))(Hpz(tBu))(2)] (6). The latter compound contains a Hpzt(Bu) ligand bridging the two Cu ions in an unusual kappa(1),mu-coordination mode. The variable temperature magnetic properties of 1-3 show antiferromagnetic behavior, leading to a S=1/2 ground state in which the seven copper(II) ions are associated into three mutually independent distinct spin systems. In confirmation of this interpretation, Q-band EPR spectra of solid 1 and 2 at 5 K also demonstrate a S= 1/2 spin system and exhibit hyperfine coupling to three (63,65)Cu nuclei. Unusually, the coupling is manifest as an eight-line splitting of the parallel feature, rather than the usual 10 lines. This has been rationalized by a spin-projection calculation, and results from the relative magnitudes of coupling to the three Cu nuclei. UV/Vis and mass spectrometric data show that 1-4 decompose to lower nuclearity species in solution.

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“…[4][5][6][7] Substituting the (XO 4 ) 3À oxoanions (X = P, As) in the previously studied systems with the fully oxidized (VO 4 ) 3À anion has allowed new structural chemistry to be unveiled. Mixing vanadium with a second TM is particularly attractive as the resulting compounds could have potential applications in areas linked to catalysis, batteries, and magnetism.…”

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confidence: 99%

The Versatile Chemistry and Noncentrosymmetric Crystal Structures of Salt‐Inclusion Vanadate Hybrids

et al. 2008

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Hybrid solids containing chemically dissimilar components have attracted much interest in advanced materials synthesis due to their structural versatility and multifunctional properties. Metal-organic frameworks (MOFs), for instance, have been extensively explored for their potential applications in technologically important fields such as heterogeneous catalysis, gas storage, and sensors. [1][2][3] These solids are moleculebased composite materials that contain metal ions or metal ion clusters as nodes and organic ligands as linkers. Specialframework MOFs, including noncentrosymmetric (NCS) solids, can be constructed by design due to the modular nature of their structures. Salt-inclusion solids (SISs), which are a newly emerging class of hybrid compounds, are reported to exhibit covalent metal oxide frameworks integrated with ionic lattices including alkali/alkaline-earth metal halides and others such as ammonium halides. [4][5][6][7] These all-inorganic SISs possess a fascinating structural chemistry complementary to MOFs where bonding at the interface of the dissimilar components appears to be directional. This property has been revealed through the formation of salt-templated porous frameworks [6] and NCS lattices. [7] In general, SISs are synthesized in reactive molten-salt media at 100-150 K above the melting point of the salt employed. Although no reaction mechanism has been formulated, one can imagine that the metal oxides are first "dissolved" in the corrosive molten salt and then, upon cooling, the covalent lattice aggregates around the inherent structure of the molten ionic salt [8] to form the resulting special frameworks. Employing this concept, we have recently expanded our studies in saltinclusion chemistry into the vanadate and non-oxide systems, [9] and this is the first of several reports in the area of SISs of vanadium(V)-based mixed-metal oxides to depict the rich structural chemistry inherent in this system.Prior to this study, most efforts in the field of salt-inclusion synthesis had been focused on creating mixed-framework solids based on transition metal (TM) phosphates, arsenates, and silicates. [4][5][6][7] Substituting the (XO 4 ) 3À oxoanions (X = P, As) in the previously studied systems with the fully oxidized (VO 4 ) 3À anion has allowed new structural chemistry to be unveiled. Mixing vanadium with a second TM is particularly attractive as the resulting compounds could have potential applications in areas linked to catalysis, batteries, and magnetism. This is in part due to the variable crystal chemistry of the added transition metals as well as the utility of the unique frameworks created by the salt. Structurally, like their silicate counterparts, fully oxidized vanadium(V) compounds could achieve more diversity due to their ability to form vanadate units of varying size, shape, and geometry, such as dimers, trimers, chains, and rings. Unlike Si, P, and As, however, V can adopt several different coordination modes and can therefore achieve even greater structural versatility. Furt...

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Supramolekulare Anorganische Chemie: von Gästen in kleinen und großen Wirten

Cited by 136 publications

References 213 publications

Anion‐Templated Synthesis

Anion‐Templated Synthesis

Reactions of Copper(II) Salts with 3{5}‐tert‐Butylpyrazole: Double‐Cubane Complexes with Bound Exogenous Anions, and a Novel Pyrazole Coordination Mode

The Versatile Chemistry and Noncentrosymmetric Crystal Structures of Salt‐Inclusion Vanadate Hybrids

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