Hydrogen-Bond Directed 1D and 3D Cyanide-Bridged Heterometallic Complexes: Synthesis, Crystal Structures and Magnetic Properties

Abstract

By employing K2[Pd(CN)4] as building block, [Mn(L)(H2O)2]ClO4 or Mn(Phen)2Cl2 (L = N,N-ethylene-bis(3-methoxysalicylideneiminate; Phen = 1,10-phenanthroline) as assembling segment, a trinuclear cyanide-bridged heterometallic Pd(II)-Mn(III) complex {[Mn(L)(H2O)]2[Pd(CN)4]}2·4H2O (1) and a ion-pair complex [Mn(Phen)2(H2O)2][Pd(CN)4] (2) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single X-ray diffraction analysis reveals the cyanide-bridged trinuclear complex 1 is self-complementary through coordinated aqua ligands from one complex and the free O4 compartments from the neighboring complex, therefore giving 1D single chain supramolecular structure. For complex 2, it is constructed into interesting 3D network depending on the intermolecular O···H–N hydrogen bond interactions. Investigation over magnetic susceptibility of complex 1 reveals the overall weak antiferromagnetic coupling between the adjacent Mn(III) ions. With [Pd(CN)4]2− as cyanide building block and bicompartimental schiff-base manganese(III) compound or Mn(II)-phenanthroline compound as assembling segment, one heterobimetallic cyanide-bridged trinuclear clusters and one heterobimetallic ion-pair complex have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray structure determination, in which the trinuclear complex 1 is self-assembled into one-dimensional chain structure by the intermolecular O–H⋯O hydrogen bond interactions, while the ion-pair complex 2 is linked into interesting three-dimensional network supramolecular structure by the intermolecular O–H⋯N hydrogen bond interactions. The trinuclear structure (top) and 1D single chain structure (bottom) constructed by intermolecular hydrogen bond interactions for complex 1. The crystal structure of ion-pair complex 2 (top) and its three-dimensional supramolecular structure constructed by intermolecular O-H⋯N hydrogen bond interactions (a axis (top), b axis (middle), c axis (bottom)). The magnetic property of complex 1.