Supracluster Assembly of Archimedean Cages with 72 Hydrogen Bonds for the Aldol Addition Reaction

• Published in: Angewandte Chemie 2023-12, Vol.135 (49), p.n/a
• Main Authors: Liu, Ya‐Jie, Su, Hai‐Feng, Sun, Yi‐Fan, Wang, San‐Tai, Zhang, Cheng‐Yang, Fang, Wei‐Hui, Zhang, Jian
• Format: Article
• Language: English
• Subjects: Aldehydes; Assembly; Bonding strength; Brucite; Catalysis; Catechol; Chemical synthesis; Chemistry; Cluster Science; Clusters; Condensates; Hierarchical Assembly; Hydrogen; Hydrogen bonding; Hydrogen bonds; Ionization; Isomers; Magnesium hydroxide; Mass spectrometry; Mass spectroscopy; Nanoparticles; Structure-function relationships; Supracluster; Zeolite
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202309971

Clusters that can be experimentally precisely characterized and theoretically accurately calculated are essential to understanding the relationship between material structure and function. Here, we propose the concept of “supraclusters”, which aim to connect “supramolecules” and “suprananoparticles” as well as reveal the unique assembly behavior of “supraclusters” with nanoparticle size at the molecular level. The implementation of supraclusters is full of challenges due to the difficulty in satisfying the ordered connectivity of clusters due to their abundant and dispersed hydrogen bonding sites. By solvothermal synthesis under a high catechol (H2CATs) content, we successfully isolated a series of triangular {Al6M3} cluster compounds possessing brucite‐like structural features. Interestingly, eight {Al6M3} clusters form 72‐fold strong hydrogen bonding truncatedhexahedron Archimedean {Al6M3}8 supracluster cage (abbreviated as H‐tcu). Surprisingly, the solution stability of the H‐tcu was further proved by electrospray ionization mass spectrometry (ESI‐MS) characterization. Therefore, it is not difficult to explain the reason for assembly of H‐tcu into edge‐directed and vertex‐directed isomers. These porous supraclusters can be obtained by scale‐up synthesis and exhibit a noticeable catalysis effect towards the condensation of acetone and p‐nitrobenzaldehyde. As an intermediate state of supramolecule and suprananoparticle, the supracluster assembly can enrich the cluster chemistry and bring new structural types. Al−O clusters‐based supraclusters presenting multiple hydrogen‐bonded porous assemblies can offer outstanding catalysis ability both in the homogeneous and heterogeneous phases. The supracluster proposed here will build a bridge between “supramolecule” and “supraparticle”, and provide new perspectives for synthesizing zeolite‐like materials.