Crystallization method controlled trinuclear or ion-pair Manganese(III)-porphyrin-based heterobimetallic complexes: Synthesis, spectra characterization, and crystal structure

Cyanide-bridged trinuclear heterometallic Ag(I)-Mn(III) complex {[Mn(TClPP)(H2O)](2)[Ag(CN)(2)]}(2) center dot 2Br center dot 2C(3)H(6)O center dot 3H(2)O (I) and ion-pair complex {[Mn(TClPP)(CH3OH)(2)][Ag(CN)(2)]} center dot 0.5H(2)O (II) have been synthesized with [Mn(TClTPP)(H2O)(2)]Br (H2TClTPP = meso-tetra(4-chlorophenyl)porphyrin) as assembling segment and K[Ag(CN)(2)] as building block by using different crystallization method. These two complexes have been characterized by elemental analysis, IR spectroscopy and X-ray structure determination. In the trinuclear complex I, [Ag(CN)(2)](-) as bidentate ligand coordinates with the two central Mn(III) atom of [Mn(TClPP)(H2O)(2)](+) through its two trans cyanide groups to form the complex cation of [Mn(TClPP)(H2O)](2)[Ag(CN)(2)](+), which further constructs the neutral complexes with the help of one Br- as balanced anion. For the ion-pair complex II composed by free [Mn(TClPP)(CH3OH)(2)](+) cation and free [Ag(CN)2](-) anion, it can be linked into one-dimensional supramolecular structure with the dependence of the intermolecular O-H...N and O-H...O hydrogen bond interactions.