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 functionatized materials retained high crystallinty and were permanently porous with high surface areas [3200 and 1700 m(2)g(-1) for (Zn4O)(3)(BDC-C6H5N2)(3)(BTB)(4) and (Zn4O)(3)(BDC-C6H5N2PdCl2)(3)(BTB)(4), respectively.]