Dimension Increase via Hierarchical Hydrogen Bonding from Simple Pincer-like Mononuclear complexes

A tetradentate symmetric ligand bearing both coordination and hydrogen bonding sites, N1,N3-bis(1-(1H-benzimidazol-2-yl)-ethylidene)propane-1,3-diamine (H2bbepd) was utilized to synthesize a series of transition metal complexes, namely [Co(H2bbepd)(H2O)2]·2ClO4 (1), [Cu(H2bbepd)(OTs-)]·OTs- (2),[Cu(bbepd)(CH3OH)] (3), [Cd(H2bbepd)(NO3)2]·CH3OH (4), [Cd(H2bbepd)(CH3OH)Cl]·Cl (5), and [Cd(bbepd)(CH3OH)2] (6). These complexes show similar discrete pincer-like coordination units, possessing different arrangements of hydrogen bonding donor and acceptor sites. With or without the aid of uncoordinated anions and solvent molecules, such mononuclear units have been effectively involved in the construction of hierarchical hydrogen bonding assemblies (successively via level I and level II), leading to discrete binuclear ring (complex 2), one-dimensional chain or ribbon (complexes 3, 4 and 6) and two-dimensional layer (complexes 1 and 5) aggregates.