Benzene-induced hydro(solvo)thermal synthesis of Cu2+ and Zn2+ coordination polymers based on 1,3-benzenedicarboxylate

Hydro(solvo)thermal reactions of Cu(NO3)2·2.5H2O or Zn(NO3)2·6H2O with 1,3-H2bdc provided two structurally different coordination polymers; a 2D network “metallacalixarene” based on the paddlewheel-type cluster with the formula [Cu(1,3-bdc)·H2O]·H2O (1) and a 3D framework [Zn(1,3-bdc)] (2), respectively. The use of a base was unnecessary in this synthesis; however, the presence of benzene played a crucial role in the crystallization of the desired products and could act as a template molecule in the synthesis of polymer (1). The unsaturated apical sites in the Cu2 cluster of polymer (1) were occupied by water molecules, what consequently led to the structural decomposition of the framework after exposing the sample in air, which was not the case of the Zn-coordination polymer (2).