Tetraphenylmethane has emerged as a recurrent building block for advanced porous materials such as COFs, PAFs and hypercrosslinked polymers. Guided by a similar design principle, we have previously synthesized shape-persistent dendrimers with tetraphenylmethane nodes and ethynylene linkers. Here we report the generality of our approach by describing new dendritic architectures built from tetraphenylmethane. First, we prepared expanded dendrimers where the tetrahedral units are bonded through larger rigid rod spacers. Among the different synthetic strategies tested, the convergent route, with alternating steps of Pd-catalyzed Sonogashira coupling and alkyne activation by removal of TMS masking groups, efficiently afforded the first- and second-generation dendrimers. A second type of compounds having a linear diyne at the core is also described. The dendrimers of generations 1-2 were also synthesized by a convergent approach, with the diyne being assembled in the last step of the synthesis by a Glaser oxidative homocoupling of the corresponding dendrons bearing a terminal alkyne at the focal point. A third-generation dendrimer was also successfully prepared by a double-phase strategy.<br>
Alkyl‐Linked Porphyrin Porous Polymers for Gas Capture and Precious Metal Adsorption