Jingzhe Li, Fan Dong, Manchang Kou, Shengbin Zhou, Xiaoyu Huang, Meilin Wu, Yu Tang, Xiaoliang Tang* and Weisheng Liu,
{"title":"构建具有中空壁腔和大窗口的镧系元素笼,促进亲核加成反应","authors":"Jingzhe Li, Fan Dong, Manchang Kou, Shengbin Zhou, Xiaoyu Huang, Meilin Wu, Yu Tang, Xiaoliang Tang* and Weisheng Liu, ","doi":"10.1021/acs.chemmater.4c0225210.1021/acs.chemmater.4c02252","DOIUrl":null,"url":null,"abstract":"<p >Metal–organic cages (MOCs) as artificial mimic enzymes can allow small organic molecules to freely move in and out of the cavity with confined space, which often can increase intermolecular collisions and accelerate those reactions that are difficult to occur. This kind of homogeneous catalyst possesses high catalytic activity and regioselectivity, attracting growing interest recently. However, the rational design of MOCs with large openings as well as rich active sites for efficient chemical conversions remains a great challenge. Herein, we report a decanuclear 3d-4f MOC, <b>Zn</b><sub><b>2</b></sub><b>Yb</b><sub><b>8</b></sub>, with a hollow-walled cavity and four large windows self-assembled cooperatively by bridging ligands, Zn-based metalloligands, and lanthanide Yb<sup>3+</sup> ions. The lantern-like <b>Zn</b><sub><b>2</b></sub><b>Yb</b><sub><b>8</b></sub> not only exposes unblocked passageways for allowing more guest molecules to penetrate the cage smoothly but also provides rich Lewis centers within the cavity, which could promote nucleophilic additions to effectively boost Friedel–Crafts alkylation and the three-component Strecker reaction. With the <b>Zn</b><sub><b>2</b></sub><b>Yb</b><sub><b>8</b></sub> catalyst, more than 13 bis(indolyl)methane derivatives could be synthesized easily in 53–98% through Friedel–Crafts alkylation, and the conversion of the Strecker reaction for aniline, benzaldehyde, and trimethylsilyl cyanide could achieve approximately 98% in 3 h. Furthermore, host–guest relationship investigations confirmed that the catalytic function of the <b>Zn</b><sub><b>2</b></sub><b>Yb</b><sub><b>8</b></sub> cage could be mainly attributed to the synergy of the inherent confinement effect, multiple Lewis catalytic sites, and host–guest electrostatic interactions in the coordination cage. The construction of the discrete 3d-4f MOC with large windows and its catalytic applications in nucleophilic additions may represent a potential approach for developing enzyme-like supramolecular nanoreactors.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 21","pages":"10699–10709 10699–10709"},"PeriodicalIF":7.2000,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Construction of a Lanthanide Cage with a Hollow-Walled Cavity and Large Windows to Promote Nucleophilic Additions\",\"authors\":\"Jingzhe Li, Fan Dong, Manchang Kou, Shengbin Zhou, Xiaoyu Huang, Meilin Wu, Yu Tang, Xiaoliang Tang* and Weisheng Liu, \",\"doi\":\"10.1021/acs.chemmater.4c0225210.1021/acs.chemmater.4c02252\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Metal–organic cages (MOCs) as artificial mimic enzymes can allow small organic molecules to freely move in and out of the cavity with confined space, which often can increase intermolecular collisions and accelerate those reactions that are difficult to occur. This kind of homogeneous catalyst possesses high catalytic activity and regioselectivity, attracting growing interest recently. However, the rational design of MOCs with large openings as well as rich active sites for efficient chemical conversions remains a great challenge. Herein, we report a decanuclear 3d-4f MOC, <b>Zn</b><sub><b>2</b></sub><b>Yb</b><sub><b>8</b></sub>, with a hollow-walled cavity and four large windows self-assembled cooperatively by bridging ligands, Zn-based metalloligands, and lanthanide Yb<sup>3+</sup> ions. The lantern-like <b>Zn</b><sub><b>2</b></sub><b>Yb</b><sub><b>8</b></sub> not only exposes unblocked passageways for allowing more guest molecules to penetrate the cage smoothly but also provides rich Lewis centers within the cavity, which could promote nucleophilic additions to effectively boost Friedel–Crafts alkylation and the three-component Strecker reaction. With the <b>Zn</b><sub><b>2</b></sub><b>Yb</b><sub><b>8</b></sub> catalyst, more than 13 bis(indolyl)methane derivatives could be synthesized easily in 53–98% through Friedel–Crafts alkylation, and the conversion of the Strecker reaction for aniline, benzaldehyde, and trimethylsilyl cyanide could achieve approximately 98% in 3 h. Furthermore, host–guest relationship investigations confirmed that the catalytic function of the <b>Zn</b><sub><b>2</b></sub><b>Yb</b><sub><b>8</b></sub> cage could be mainly attributed to the synergy of the inherent confinement effect, multiple Lewis catalytic sites, and host–guest electrostatic interactions in the coordination cage. 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Construction of a Lanthanide Cage with a Hollow-Walled Cavity and Large Windows to Promote Nucleophilic Additions
Metal–organic cages (MOCs) as artificial mimic enzymes can allow small organic molecules to freely move in and out of the cavity with confined space, which often can increase intermolecular collisions and accelerate those reactions that are difficult to occur. This kind of homogeneous catalyst possesses high catalytic activity and regioselectivity, attracting growing interest recently. However, the rational design of MOCs with large openings as well as rich active sites for efficient chemical conversions remains a great challenge. Herein, we report a decanuclear 3d-4f MOC, Zn2Yb8, with a hollow-walled cavity and four large windows self-assembled cooperatively by bridging ligands, Zn-based metalloligands, and lanthanide Yb3+ ions. The lantern-like Zn2Yb8 not only exposes unblocked passageways for allowing more guest molecules to penetrate the cage smoothly but also provides rich Lewis centers within the cavity, which could promote nucleophilic additions to effectively boost Friedel–Crafts alkylation and the three-component Strecker reaction. With the Zn2Yb8 catalyst, more than 13 bis(indolyl)methane derivatives could be synthesized easily in 53–98% through Friedel–Crafts alkylation, and the conversion of the Strecker reaction for aniline, benzaldehyde, and trimethylsilyl cyanide could achieve approximately 98% in 3 h. Furthermore, host–guest relationship investigations confirmed that the catalytic function of the Zn2Yb8 cage could be mainly attributed to the synergy of the inherent confinement effect, multiple Lewis catalytic sites, and host–guest electrostatic interactions in the coordination cage. The construction of the discrete 3d-4f MOC with large windows and its catalytic applications in nucleophilic additions may represent a potential approach for developing enzyme-like supramolecular nanoreactors.
期刊介绍:
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.