By using the steric hindrance of the nonplanar linker, the connectivity of Zr<sub>6</sub> node can be tuned from 8-c to unusual 4-c. Further, through either one-pot synthesis or postsynthetic linker installation strategies, the connectivity of Zr<sub>6</sub> node can be tuned from 8-c to 10-c by the insertion of a secondary linear dicarboxylate linker, from which not only the temperature-dependent flexibility of the structure can be effectively controlled with enhanced rigidity and thermal stability but also a scaffold for postsynthetic metalation of Pd(II) catalyst for Heck coupling reaction is offered.