西班牙瓦伦西亚大学Carlos Marti-Gastaldo团队揭示了等网状异金属钛有机骨架中二胺的选择性注入协同催化策略。 相关研究成果发表在2021年2月25日出版的《德国应用化学》。

研究人员介绍了第一个等网状钛-有机骨架的例子MUV-10和MUV-12，以说明如何利用硬Ti（IV）和软Ca（II）金属位点的不同亲和力将胺选择性接枝到最后一个骨架上。这使得Lewis酸钛中心和两个相当大的孔中可用的NH2位点结合起来，以便在室温和大气压下将CO2协同环加成到环氧化物中。

分子选择性地接枝到异质金属簇合物上，构成了一个方法库，可用于控制孔隙化学确定性控制所需框架精确位置上化学功能的定位和分布。

附：英文原文

Title: Selective implantation of diamines for cooperative catalysis in isoreticular heterometallic titanium‐organic frameworks

Author: Elena L, Natalia M. Padial, Javier Castells-Gil, Carolina R. Ganivet, Ana Rubio-Gaspar, Francisco G. Cirujano, Neyvis Almora-Barrios, Sergio Tatay, Sergio Naval, Carlos Marti-Gastaldo

Issue&Volume: 2021-02-25

Abstract: We introduce the first example of isoreticular titanium‐organic frameworks, MUV‐10 and MUV‐12, to show how the different affinity of hard Ti(IV) and soft Ca(II) metal sites can be used to direct selective grafting of amines to the last.  This enables the combination of Lewis acid titanium centers and available  ‐NH2    sites in two sizeable pores for cooperative cycloaddition of CO2   to epoxides at room temperature and atmospheric pressure. The s elective grafting of molecules to heterometallic clusters  adds up to the pool of methodologies available for controlling the positioning and distribution of chemical functions in precise positions of the framework required for definitive control of pore chemistry.

DOI: 10.1002/anie.202100176

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202100176