Liu Ya-Jie, Yu Yinghua, Sun Yi-Fan, Fang Wei-Hui, Zhang Jian
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences 350002 Fuzhou P. R. China
University of Chinese Academy of Sciences Beijing 100049 P. R. China.
Chem Sci. 2022 Apr 19;13(19):5693-5700. doi: 10.1039/d2sc00526c. eCollection 2022 May 18.
Heterometallic cluster-based framework materials are of interest in terms of both their porous structures and multi-metallic reactivity. However, such materials have not yet been extensively investigated because of difficulties in their synthesis and structural characterization. Herein, we reported the designable synthesis of atomically precise heterometallic cluster-based framework compounds and their application as catalysts in aldol reactions. By using the synergistic coordination protocol, we successfully isolated a broad range of compounds with the general formula, [AlMO(L)(DABCO)] (L = carboxylates; DABCO = 1,4-diazabicyclo[2.2.2]-octane; M = Co, Mn, Zn, Fe, Cd). The basic heterometallic building blocks contain unprecedented main-group γ-alumina moieties and surrounding unsaturated transition metal centers. Interestingly, the porosity and interpenetration of these frameworks can be rationally regulated through the unprecedented strategy of increment of the metal radius in addition to general introduction of sterically bulky groups on the ligand. Furthermore, these porous materials are effective catalysts for aldol reactions. This work provides a catalytic molecular model platform with accurate molecular bonding between the supporters and catalytically active metal ions.
基于异金属簇的框架材料因其多孔结构和多金属反应性而备受关注。然而，由于其合成和结构表征困难，此类材料尚未得到广泛研究。在此，我们报道了原子精确的基于异金属簇的框架化合物的可设计合成及其在醛醇缩合反应中作为催化剂的应用。通过使用协同配位方案，我们成功分离出了一系列通式为[AlMO(L)(DABCO)]的化合物（L = 羧酸盐；DABCO = 1,4 - 二氮杂双环[2.2.2]辛烷；M = Co、Mn、Zn、Fe、Cd）。基本的异金属结构单元包含前所未有的主族γ - 氧化铝部分和周围的不饱和过渡金属中心。有趣的是，除了在配体上普遍引入空间位阻较大的基团外，通过前所未有的增加金属半径的策略，可以合理调控这些框架的孔隙率和互穿情况。此外，这些多孔材料是醛醇缩合反应的有效催化剂。这项工作提供了一个催化分子模型平台，在载体和催化活性金属离子之间具有精确的分子键合。
