LAUSR

We attempted the synthesis and crystallographic characterization of light-metal coordination polymers (CPs) using a 4-(methylsulfonyl)benzoate (msbza–) ligand with a charge-polarized neutral methylsulfonyl coordination moiety, in order to diversify the limited structures of light-metal CPs, as compared with heavy-metal CPs. As expected from the results of DFT calculations, all of the obtained CPs {three-dimensional (3D) [Mg2Na2(msbza)6(H2O)3]n (1), two-dimensional (2D) [KH(msbza)2]n (2) and 2D [Na(msbza)]n (3)} exhibited coordination of the methylsulfonyl moiety to light-metal cations, in addition to coordination of the carboxylate. These structural features suggest that the use of a neutral methylsulfonyl coordination site is a powerful tool for the structural diversification of light-metal CPs. In addition, the 3D CP 1, with the rare and unique tetranuclear Mg2Na2 secondary building unit, showed an unprecedented single-crystal-to-single-crystal transformation via the low-crystalline state.