Selective Implantation of Diamines for Cooperative Catalysis in Isoreticular Heterometallic Titanium-Organic Frameworks

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. This enables the combination of Lewis acid titanium centers and available -NH, sites in two sizeable pores for cooperative cycloaddition of CO2 to epoxides at room temperature and atmospheric pressure. The selective 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.

Automated summary

The study demonstrates how the different affinity of metal sites can be utilized for selective grafting of molecules, allowing for cooperative reactions between Lewis acid titanium centers and available -NH sites in the framework. This approach provides a method for controlling the positioning and distribution of chemical functions in precise locations for cooperative reactions of epoxides and CO2.