Accurate binding of porous aluminum molecular ring catalysts with the substrate

Luo, Dan; Han, Xiao; Zhang, Minyi; Li, Shangda; Li, He; Hong, Lu; Li, Chunsen; Lin, Qipu; Fang, Wei‐Hui; Zhang, Jian

doi:10.1039/d3sc01260c

Cited by 8 publications

(10 citation statements)

References 65 publications

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“…We tested the TGA-DSC of three Al 8 rings without DES components (AlOC-15, AlOC-58, and AlOC-59) for comparison to determine the role of DES in melting. [24,37] First, no significant phase transition was observed in the TGA-DSC curves of these compounds (Figure S33). The crystal shape after heating was regular.…”

Section: Resultsmentioning

confidence: 98%

Meltable Aluminum Molecular Rings with Fluorescence and Nonlinear Optical Properties

Wang,

Fang,

Zhang

2024

Angewandte Chemie

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Crystal−liquid−glass, which combines the tunable properties of crystalline compounds with the processability of glasses, has emerged as a new class of materials for fabricating bulk‐shapable devices in real applications. Inspired by the characteristics of deep eutectic solvent (DES) mixtures involving significant depressions in melting points compared to their neat constituent components, in this study, we designed and synthesized the first examples of meltable aluminum oxo clusters (AlOCs) via lattice doping with DESs at the molecular level. The abundant and strong hydrogen bonding between the aluminum molecular ring, DES components, and lattice solvents is postulated to be the root that affords melting point depressions and, thus, “melting” clusters. We prepared a transparent bubble‐free glass film under autogenous pressure using a hot‐press method. These cluster‐based films exhibited luminescent and nonlinear optical properties similar to those of pristine crystalline compounds. Our study belongs to the interdisciplinary disciplines of chemistry and physics. It not only breaks the limitations of crystalline glass on metal and ligand types but also acts as a general guide for extending the range of meltable crystalline materials.

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Section: Resultsmentioning

confidence: 98%

Meltable Aluminum Molecular Rings with Fluorescence and Nonlinear Optical Properties

Wang,

Fang,

Zhang

2024

Angewandte Chemie

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“…2i). [38][39][40][41][42][43][44] In solvent systems containing conjugated ligands, phenols with stronger polarity can easily interact with them via π⋯π interaction, thereby distorting the Al 16 nucleus. This is also the reason why the amount of the linker phenol (20) is greater than that of n-propanol (16).…”

Section: Ring Curvature Discussionmentioning

confidence: 99%

Two solvent-dependent Al₁₆ nanorings: design, synthesis and nonlinear optical limiting behavior

Wang,

Qi,

Chen

et al. 2024

Inorg. Chem. Front.

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“…Since the organic shell provides weak interaction sites, clusters can be assembled to form stable isomers by different noncovalent interactions (hydrogen bonds or π•••π interactions) during crystallization. 2,38,40 For example, AlOC-22 and AlOC-26NC have the same molecular formula (Al 8 . Since the organic shell provides weak interaction sites, clusters can be assembled to form stable isomers by different noncovalent interactions (hydrogen bonds or π•••π interactions) during crystallization.…”

Section: Noncovalent Assembly Of Aluminum Molecular Ringsmentioning

confidence: 99%

“…Since the organic shell provides weak interaction sites, clusters can be assembled to form stable isomers by different noncovalent interactions (hydrogen bonds or π•••π interactions) during crystallization. 2,38,40 For example, AlOC−22 and AlOC−26NC isomers have the same molecular formula (Al 8 (PZ−CH 3 ) 8 (OH) 8 BA 8 ). They crystallized in tetragonal P 4 /nnc to form nanotube arrays and cubic P432 to generate nanocage structures, respectively.…”

Section: Noncovalent Assembly Of Aluminum Molecular Ringsmentioning

confidence: 99%

“…In 2023, our group synthesized two aluminum molecular rings with porous nanocage and nanotube structures using N-substituted aromatic carboxylate ligands. 40 The regular and dense Al 3+ and N sites can serve as Lewis acid and base sites, respectively, to effectively catalyze the cyanosilylation reactions. The binding sites between aluminum molecular rings and substrates can be crystallographically characterized and theoretically confirmed, providing a reliable basis for understanding the mechanism of cyanosilylation.…”

Section: Catalytic Performancesmentioning

confidence: 99%

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Induced Aggregation, Solvent Regulation, and Supracluster Assembly of Aluminum Oxo Clusters

Fang,

Xie,

Wang

et al. 2024

Acc. Chem. Res.

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Metrics & MoreArticle RecommendationsCONSPECTUS: Recent years have witnessed the development of cluster materials as they are atomically precise molecules with uniform size and solution-processability, which are unattainable with traditional nanoparticles or framework materials. The motivation for studying Al(III) chemistry is not only to understand the aggregation process of aluminum in the environment but also to develop novel low-cost materials given its natural abundance. However, the Al-related clusters are underdeveloped compared to the coinage metals, lanthanides, and transition metals. The challenge in isolating crystalline compounds is the lack of an effective method to realize the controllable hydrolysis of Al(III) ions. Compared with the traditional hydrolysis of inorganic Al(III) salts in highly alkaline solutions and hydrolysis of aluminum trialkyl compounds conducted carefully in an inert operating environment, we herein developed an effective way to control the hydrolysis of aluminum isopropanol through an alcoxalation reaction. By solvothermal/low melting point solid melting synthesis and using "ligand aggregation, solvent regulation, and supracluster assembly" strategies, our laboratory has established an organic-inorganic hybrid system of aluminum oxo clusters (AlOCs). The employment of organic ligands promotes the aggregation and slows the hydrolysis of Al(III) ions, which in turn improves the crystallization process. The regulation of the structure types can be achieved through the selection of ligands and the supporting solvents. Compared with the traditional condensed polyoxoaluminates, we successfully isolated a broad range of porous AlOCs, including aluminum molecular rings and Archimedes aluminum oxo cages. By studying ring expansion, structural transformation, and intermolecular supramolecular assembly, we demonstrate unique and unprecedented structural controllability and assembly behavior in cluster science. The advancement of this universal synthetic method is to realize materials customization through modularly oriented supracluster assembly. In this Account, we will provide a clear-cut definition and terminology of "ligand aggregation, solvent regulation, and supracluster assembly". Then we will discuss the discovery in this area by using a strategy, such as aluminum molecular ring, ring size expansion, ring supracluster assembly, etc. Furthermore, given the internal and external pore structures, as well as the solubility and modifiability of the AlOCs, we will demonstrate their potential applications in both the solid and liquid phases, such as iodine capture, the optical limiting responses, and dopant in polymer dielectrics. The strategy herein can be applied to extensive cluster science and promote the research of main group element chemistry. The new synthetic method, fascinating clusters, and unprecedented assembly behaviors we have discovered will advance Al(III) chemistry and will also lay the foundation for functional applications.

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Accurate binding of porous aluminum molecular ring catalysts with the substrate

Abstract: Metal molecular rings are a class of compounds with aesthetically pleasing symmetry and fundamentally useful properties. The reported work generally focuses on the ring center cavity, and there is litter...

Cited by 8 publications

References 65 publications

Meltable Aluminum Molecular Rings with Fluorescence and Nonlinear Optical Properties

Meltable Aluminum Molecular Rings with Fluorescence and Nonlinear Optical Properties

Two solvent-dependent Al₁₆ nanorings: design, synthesis and nonlinear optical limiting behavior

Induced Aggregation, Solvent Regulation, and Supracluster Assembly of Aluminum Oxo Clusters

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Accurate binding of porous aluminum molecular ring catalysts with the substrate

Abstract: Metal molecular rings are a class of compounds with aesthetically pleasing symmetry and fundamentally useful properties. The reported work generally focuses on the ring center cavity, and there is litter...

Cited by 8 publications

References 65 publications

Meltable Aluminum Molecular Rings with Fluorescence and Nonlinear Optical Properties

Meltable Aluminum Molecular Rings with Fluorescence and Nonlinear Optical Properties

Two solvent-dependent Al16 nanorings: design, synthesis and nonlinear optical limiting behavior

Induced Aggregation, Solvent Regulation, and Supracluster Assembly of Aluminum Oxo Clusters

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Two solvent-dependent Al₁₆ nanorings: design, synthesis and nonlinear optical limiting behavior