Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment.

The reaction of anhydrous lanthanide chlorides together with 4,4'-bipyridine yields the MOFs 2∞[Ln2Cl6(bipy)3]·2bipy, with Ln = Pr - Yb, bipy = 4,4'-bipyridine, and 3∞[La2Cl6(bipy)5]·4bipy. Post-synthetic thermal treatment in combination with different vacuum conditions was successfully used to shape the porosity of the MOFs. In addition to the MOFs microporosity, a tuneable mesoporosity can be implemented depending on the treatment conditions as a surface morphological modification. Furthermore, thermal treatment without vacuum results in several identifiable crystalline high-temperature phases. Instead of collapse of the frameworks upon heating, further aggregation under release of bipy is observed. 3∞[LaCl3(bipy)] and 2∞[Ln3Cl9(bipy)3], with Ln = La, Pr, Sm, and 1∞[Ho2Cl6(bipy)2] were identified and characterized, which can also exhibit luminescence. Besides being released upon heating, the linker 4,4'-bipyridine can undergo activation of C-C bonding in ortho-position leading to the in-situ formation of 4,4':2',2'':4'',4'''-quaterpyridine (qtpy). qtpy can thereby function as linker itself, as shown for the formation of the network 2∞[Gd2Cl6(qtpy)2(bipy)2]·bipy. Altogether, the manuscript elaborates the influence of thermal treatment beyond the usual activation procedures reported for MOFs.