Coordination polymers of alkali metal cyclosiloxazanides with one- and two-dimensional structures

Jost, Maximilian; Richter, Roman-Malte; Balmer, Michael; Peters, Bertram; Dankert, Fabian; Hänisch, Carsten von

doi:10.1039/d0dt01060j

Cited by 5 publications

(4 citation statements)

References 25 publications

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“…The same could be said regarding screening ethanol solvate and coordinating rubidium ions. This also prevents the formation of the coordination polymer structure despite the significant coordinative potential of rubidium centers towards siloxanes, which could be fruitful in supramolecular assembly [ 25 , 68 , 69 , 70 ].…”

Section: Resultsmentioning

confidence: 99%

Cagelike Octacopper Methylsilsesquioxanes: Self-Assembly in the Focus of Alkaline Metal Ion Influence—Synthesis, Structure, and Catalytic Activity

et al. 2023

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A family of unusual octacopper cage methylsilsesquioxanes 1–4 were prepared and characterized. Features of their cagelike (prismatic) structure were established using X-ray diffraction studies. Effects of distortion of prismatic cages 1–4 due to variation of (i) additional alkaline metal ions (K, Rb, or Cs), (ii) combination of solvating ligands, and (iii) nature of encapsulating species were found. Opportunities for the design of supramolecular 1D extended structures were found. These opportunities are based on (i) formate linkers between copper centers (in the case of Cu8K2-based compound 2) or (ii) crown ether-like contacts between cesium ions and siloxane cycles (in the case of Cu8Cs2-based compound 4). Cu8Cs2-complex 4 was evaluated in the catalysis of alkanes and alcohols. Complex 4 exhibits high catalytic activity. The yield of cyclohexane oxidation products is 35%. The presence of nitric acid is necessary as a co-catalyst. The oxidation of alcohols with the participation of complex 4 as a catalyst and tert-butyl hydroperoxide as an oxidizer also proceeds in high yields of up to 98%.

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Section: Resultsmentioning

confidence: 99%

Cagelike Octacopper Methylsilsesquioxanes: Self-Assembly in the Focus of Alkaline Metal Ion Influence—Synthesis, Structure, and Catalytic Activity

et al. 2023

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“…The obtained findings enrich the coordination and supramolecular chemistry of cagelike metallasilsesquioxanes with novel, versatile building blocks and linkers. Furthermore, the main results bring new knowledge to the coordination chemistry of cyclic siloxanes and large alkali-metal ions, which can be used in future studies to design metal–organic architectures for targeted applications. − Further research on assembling novel types of copper-based complexes and the respective coordination polymers and exploring their catalytic potential are currently in progress in our laboratories.…”

Section: Discussionmentioning

confidence: 97%

Exploring Cagelike Silsesquioxane Building Blocks for the Design of Heterometallic Cu₄/M₄Architectures

Bilyachenko

Astakhov

Kulakova

et al. 2022

Crystal Growth & Design

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Within the sweeping research on the design of new coordination polymers and related metal−organic architectures, the use of silsesquioxane derivatives as important organosilicon building blocks has been poorly explored, despite a number of unique structural and functional characteristics of the resulting products. The present study thus describes an extended series (eight examples) of heterometallic Cu 4 Cs 4 and Cu 4 Rb 4 coordination polymers with the common formula [(PhSiO 1.5 ) 12 (CuO) 4 -(AO 0.5 ) 4 (Solv) x ] n •nSolv (A is Cs or Rb; Solv refers to ligands and/ or solvate molecules including H 2 O, EtOH, BuOH, DMF, and DMSO in various combinations), which are based on cagelike coppersilsesquioxanes as nontrivial secondary building units. The concept of supramolecular design was implemented in a straightforward way by the assembly of coppersilsesquioxane cages using large and coordination-versatile cesium or rubidium cations. The structures of all products were established by single-crystal X-ray diffraction studies mainly using synchrotron radiation. The resulting Cu 4 Cs 4 -and Cu 4 Rb 4 -silsesquioxanes exhibit an extracage location of the alkali-metal cations, which enables the interconnectivity of neighboring cages into 1D, 2D, or 3D coordination polymer architectures. The unique feature of such architectures is a realization of metallocene Cs•••π (Rb•••π) joints, providing tightly connected nonporous coordination polymers. A topological classification of cages and coordination polymer networks was performed. Some of the obtained compounds also represent the first examples of Rb-containing silsesquioxanes. The selected products were also tested as homogeneous catalysts in the oxidation and hydrocarboxylation of C 5 −C 8 cycloalkanes. This study extends the structural types of heterometallic silsesquioxane cages that can be efficiently applied to the design of functional coordination polymers.

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“…This is similar to the aforementioned silanolates. Complexes obtained in this way involve the cations Li + , [82–86] Na + , [87–89] K + , [85,87,89–91] Rb + , [89] Cs + , [87,89,92] Mg 2+ , [93] Sr 2+ , [94] Ba 2+ , [95,96] Sn 4+ , [97,98] Cr 2+/3+ , [99,100] Fe 3+ , [101] Y 3+ , [100,102] Zr 4+ , [103] Sm 2+ , [104] Tm 3+ , [105] Yb 2+ , [104,106–108] Th 4+ , [109–112] U 4+ , [109–113] and UO 2 2+ [114] . Hence, many siloxane⋅⋅⋅M n+ contacts might have been established over the years but are rather occasionally than purposefully realized.…”

Section: Siloxane Coordination Compoundsmentioning

confidence: 99%

Siloxane Coordination Revisited: Si−O Bond Character, Reactivity and Magnificent Molecular Shapes

Dankert

Hänisch

2021

Eur J Inorg Chem

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Siloxanes have evolved into a multi‐million dollar business due to their manifold of commercial and industrial applications. As siloxanes have high hydrophobicity, low basicity, high flexibility and also high chemical inertness in common, their chemistry differs significantly from that of organic ethers. The discovery of organic crown ethers, for instance, is commonly accepted as the birth of synthetic host‐guest chemistry. Regarding the chemical properties of siloxanes, cyclic siloxanes which formally resemble silicon analogues of crown ethers, have received considerably less interest in terms of their host‐guest chemistry. Hence, only little is known about siloxane coordination chemistry in the chemical community and the number of published works in this field has been very low till lately. In the last few years, the field has significantly advanced and elegant methods were established to enable the Si−O−Si unit for coordination. This review therefore summarizes the recent developments in the field, recapitulates the historical aspects of siloxane coordination chemistry and describes the specific Si−O bond character with regard to different siloxane linkages. Implications on Si−O bond activation are included and the limits of siloxane coordination are redefined.

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Coordination polymers of alkali metal cyclosiloxazanides with one- and two-dimensional structures

Abstract: One- and two-dimensional networks of alkali metal ions and silicon-based ligands were synthesised and structurally characterised.

Cited by 5 publications

References 25 publications

Cagelike Octacopper Methylsilsesquioxanes: Self-Assembly in the Focus of Alkaline Metal Ion Influence—Synthesis, Structure, and Catalytic Activity

Cagelike Octacopper Methylsilsesquioxanes: Self-Assembly in the Focus of Alkaline Metal Ion Influence—Synthesis, Structure, and Catalytic Activity

Exploring Cagelike Silsesquioxane Building Blocks for the Design of Heterometallic Cu₄/M₄Architectures

Siloxane Coordination Revisited: Si−O Bond Character, Reactivity and Magnificent Molecular Shapes

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Coordination polymers of alkali metal cyclosiloxazanides with one- and two-dimensional structures

Abstract: One- and two-dimensional networks of alkali metal ions and silicon-based ligands were synthesised and structurally characterised.

Cited by 5 publications

References 25 publications

Cagelike Octacopper Methylsilsesquioxanes: Self-Assembly in the Focus of Alkaline Metal Ion Influence—Synthesis, Structure, and Catalytic Activity

Cagelike Octacopper Methylsilsesquioxanes: Self-Assembly in the Focus of Alkaline Metal Ion Influence—Synthesis, Structure, and Catalytic Activity

Exploring Cagelike Silsesquioxane Building Blocks for the Design of Heterometallic Cu4/M4Architectures

Siloxane Coordination Revisited: Si−O Bond Character, Reactivity and Magnificent Molecular Shapes

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Exploring Cagelike Silsesquioxane Building Blocks for the Design of Heterometallic Cu₄/M₄Architectures