Fang Pu-Hao, Xing Kai, Qu Lu-Lu, Ma Zhen-Sha, Zhou Kang, Liu Xiao-Yuan
Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic University, 7098 Liuxian Blvd, Nanshan, Shenzhen, 518055, P. R. China.
School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, 221116, P. R. China.
Small. 2024 Nov;20(48):e2405540. doi: 10.1002/smll.202405540. Epub 2024 Aug 29.
The establishment of reticular chemistry has significantly facilitated the development of porous materials, especially for metal-organic frameworks (MOFs). On the other hand, as an alternative approach, in situ "one-pot" strategy has been explored as a promising approach to constructing MOFs, in which the synthesis of organic linkers and the sequential construction of MOFs are integrated into one solvothermal condition. This strategy can efficiently avoid the limitations faced in the traditional construction method, such as time-consuming organic synthesis and multiple separation and purification. Herein, inspired by the reaction of aldehydes and o-phenylenediamine and deep structural analysis of UiO-68, a series of tetra-, hexa-, and octa-topic carboxylic acids are synthesized using 2',3'-diamino-[1,1':4',1'"-terphenyl]-4,4'"-dicarboxylic acid and di-, tri-, and tetra-topic aldehydes as precursor. Then nine multicarboxylate-based zirconium MOFs (Zr-MOFs) are successfully constructed via the combination of reticular chemistry and in situ "one-pot" strategy. The resultant Zr-MOFs can be regarded as the partial face decoration of UiO-68. More importantly, the emission properties of resultant Zr-MOFs can be well controlled using aldehydes with tunable electronic structures. This work provides a new path to rational design and construction of porous materials with specific structures guided by reticular chemistry and conducted using in situ "one-pot" strategy.
网状化学的建立极大地促进了多孔材料的发展,尤其是金属有机框架材料(MOFs)。另一方面,作为一种替代方法,原位“一锅法”策略已被探索为一种有前景的构建MOFs的方法,其中有机连接体的合成与MOFs的顺序构建被整合到一个溶剂热条件中。这种策略可以有效避免传统构建方法所面临的限制,如耗时的有机合成以及多次分离和纯化。在此,受醛与邻苯二胺反应以及UiO - 68的深入结构分析的启发,以2',3'-二氨基-[1,1':4',1'"-三联苯]-4,4'"-二羧酸和二、三、四官能团醛为前体,合成了一系列四、六、八官能团羧酸。然后通过网状化学和原位“一锅法”策略的结合,成功构建了九种基于多羧酸盐的锆基金属有机框架材料(Zr - MOFs)。所得的Zr - MOFs可被视为UiO - 68的部分表面修饰。更重要的是,使用具有可调电子结构的醛可以很好地控制所得Zr - MOFs的发光性质。这项工作为由网状化学指导并采用原位“一锅法”策略进行特定结构多孔材料的合理设计和构建提供了一条新途径。