New Properties and Reactions in Self‐Assembled M<sub>6</sub>L<sub>4</sub>Coordination Cages

Fujita, Makoto; Yoshizawa, Michito

doi:10.1002/9783527621484.ch8

Cited by 8 publications

(3 citation statements)

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“…While it was envisioned that the metal centers could be further diversified to other metals with varied oxidation states, this task presented a major synthetic challenge due to the extreme sensitivity of self-assembly to changes in the structural components. Other catalytically active homogeneous host systems rarely show variability in the metal center . We report here the syntheses of catalytically active Si 4 L 6 , In 4 L 6 , and Ge 4 L 6 hosts, which were enabled by an optimized and generalizable guest exchange protocol (Figure ).…”

Section: Resultsmentioning

confidence: 99%

“…The guest exchange relies on a large excess of potassium ions to drive the binding equilibrium toward a K + -associated host, effectively overcoming the higher association constant of the cationic template. This approach has been previously employed for NMe 4 + ⊂ Ga 4 L 6 , which resulted in relatively poor recovery (36–41% yield) due to the similar solubility profiles of the host and excess KI (the K + source). , …”

Section: Resultsmentioning

confidence: 99%

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Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages

et al. 2022

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The results of quantum chemical and molecular dynamics calculations reveal that polyanionic gallium-based cages accelerate cyclization reactions of pentadienyl alcohols as a result of substrate cage interactions, preferential binding of reactive conformations of substrate/H 3 O + pairs, and increased substrate basicity. However, the increase in basicity dominates. Experimental structure−activity relationship studies in which the metal vertices and overall charge of the cage are varied confirm the model derived via calculations.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages

et al. 2022

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“…Metallosupramolecular chemistry also offers the promise of novel materials with interesting properties. Discrete metallosupramolecular assemblies, e.g., metallamacrocycles, box and cage compounds, have been used, for example, as receptors and reaction containers [5][6][7][8][9][10]. Potential applications in catalysis, gas-storage, separation, sensing, magnetism, optics and electrochemistry have often been mentioned in connection with coordination polymers [11][12][13][14][15][16][17].…”

Section: Introduction and Scopementioning

confidence: 99%

Structural Diversity of Metallosupramolecular Assemblies Based on the Bent Bridging Ligand 4,4′-Dithiodipyridine

2013

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4,4′-Dithiodipyridine (dtdp), also termed 4,4′-dipyridyldisulfide, is a bridging ligand of the 4,4′-bipyridine type. The introduction of the disulfide moiety inevitably leads to a relatively rigid angular structure, which exhibits axial chirality. More than 90 metal complexes containing the dtdp ligand have been crystallographically characterised until now. This review focuses on the preparation and structural diversity of discrete and polymeric metallosupramolecular assemblies constructed from dtdp as bridging ligands. These encompass metallamacrocycles with M 2 L 2 topology and coordination polymers with periodicity in one or two dimensions. One-dimensional coordination polymers represent the vast majority of the metallosupramolecular structures obtained from dtdp. These include repeated rhomboids, zigzag, helical and arched chains among other types. In this contribution, we make an attempt to provide a comprehensive account of the structural data that are currently available for metallosupramolecular assemblies based on the bent bridging ligand dtdp. OPEN ACCESSPolymers 2013, 5 528

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Halide‐Directed Assembly of Multicomponent Systems: Highly Ordered Au^I–Ag^I Molecular Aggregates

Koshevoy¹,

Karttunen²,

Shakirova³

et al. 2010

Angewandte Chemie

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A great deal of research in inorganic and organometallic chemistry is devoted to investigation of self-assembly processes, which spontaneously lead to formation of complex multimetallic supramolecular entities from relatively simple building blocks under mild conditions. The resulting wellordered species are of significant interest due to their fascinating structural characteristics and promising optical, electronic, or catalytic properties. [1,2] In most cases these species are prepared by a metal-ligand coordination-based strategy. However, group 11 metal ions tend to exhibit effective noncovalent metal-metal interactions, which often complicate the assembly processes and may result in formation of polymers or networks, catenanes, and polymetallic clusters. [2, 3] Hence, it is difficult to predict the structural topology of coinage metal aggregates, and controlling the system organization at the molecular or nanoscale level is a major synthetic challenge.One of the approaches to high-nuclearity coinage metal clusters is an elegant anion-templated synthesis of homometallic silver alkynyl cage compounds, which were shown to incorporate halides, [4] carbonate, [5] chromate, [6] and even polyoxometalates. [7] However, this approach is very little studied and the assembly processes of the d 10 heterometallic compounds in the presence of coordinating anions have never been investigated.In the course of our studies on coinage metal clusters [8][9][10] we . [9] This preparative route, which eventually involves cleavage of C À Cl bonds of CH 2 Cl 2 molecules as a source of chloride, was quite ineffective (yield of < 20 %). Alternatively, it was found that treatment of a stoichiometric reaction mixture with Ag + and Cl À ions results in rather fast and nearly quantitative formation of 1 (Scheme 1).The bromide-and iodide-containing congeners (2 and 3) were obtained analogously, though some addition of CHBr 3 and MeI, respectively, was necessary to decrease possible halide exchange with solvent (CH 2 Cl 2 ). Complexes 1-3 were characterized by 1 H and 31 P NMR spectroscopy. An X-ray diffraction study on 3 revealed its structure in the solid state (Figure 1). [11] The molecule consists of the heterometallic cluster [Au 9 Ag 12 (C 2 Ph) 18 I 3 ] surrounded by a cationic "belt" [Au 3 (P 3 P) 3 ] 3+ . Even though the general structural motif-a bimetallic cluster [Autriangle-has been described before, [12,13] the peculiarity of 3 resides in the central "axis" of three I À ions, which effectively directed the framework aggregation process and stabilized the resulting metal core. The IÀAg distances of 2.8330(14)-3.0173(13) suggest a significant contribution of a conventional bonding between the halide and metal ions. The AuÀ Ag contacts vary significantly from 2.7844(11) to 3.3472(11) , the longest of which involve silver ions bound to iodide ions. The average Au-Ag distance (3.02 ) and the AuÀAu bonds between the central cluster and the external "belt" (2.8813(6)-2.9055(6) ) are not exceptional and agree with the previously re...

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New Properties and Reactions in Self‐Assembled M₆L₄Coordination Cages

Cited by 8 publications

References 159 publications

Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages

Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages

Structural Diversity of Metallosupramolecular Assemblies Based on the Bent Bridging Ligand 4,4′-Dithiodipyridine

Halide‐Directed Assembly of Multicomponent Systems: Highly Ordered Au^I–Ag^I Molecular Aggregates

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New Properties and Reactions in Self‐Assembled M6L4Coordination Cages

Cited by 8 publications

References 159 publications

Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages

Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages

Structural Diversity of Metallosupramolecular Assemblies Based on the Bent Bridging Ligand 4,4′-Dithiodipyridine

Halide‐Directed Assembly of Multicomponent Systems: Highly Ordered AuI–AgI Molecular Aggregates

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Product

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New Properties and Reactions in Self‐Assembled M₆L₄Coordination Cages

Halide‐Directed Assembly of Multicomponent Systems: Highly Ordered Au^I–Ag^I Molecular Aggregates