Isoreticular Metalation of Metal−Organic Frameworks

Sequential covalent transformation and metalation were performed on (Zn4O)3(BDC-NH2)3(BTB)4 with maintenance of crystallinity and porosity. Reaction of (Zn4O)3(BDC-NH2)3(BTB)4 with 2-pyridinecarboxaldehyde in toluene at room temperature for 5 days resulted in the formation of the extended crystalline structure (Zn4O)3(BDC-C6H5N2)3(BTB)4, which possesses iminopyridine moieties covalently bound to the organic links of the framework. Subsequent reaction with PdCl2(CH3CN)2 in CH2Cl2 at room temperature for 12 h yielded the metalated metal−organic framework (Zn4O)3(BDC-C6H5N2PdCl2)3(BTB)4. Both functionalized materials retained high crystallinty and were permanently porous with high surface areas [3200 and 1700 m2 g−1 for (Zn4O)3(BDC-C6H5N2)3(BTB)4 and (Zn4O)3(BDC-C6H5N2PdCl2)3(BTB)4, respectively.]