Modeling the interactions of phthalocyanines in water: From the Cu(II)-tetrasulphonate to the metal-free phthalocyanine

Abstract

A quantum and statistical study on the effects of the ions Cu2+ and SO3− in the solvent structure around the metal-free phthalocyanine (H2Pc) is presented. We developed an ab initio interaction potential for the system CuPc–H2O based on quantum chemical calculations and studied its transferability to the H2Pc–H2O and [CuPc(SO3)4]4−–H2O interactions. The use of the molecular dynamics technique allows the determination of energetic and structural properties of CuPc, H2Pc, and [CuPc(SO3)4]4− in water and the understanding of the keys for the different behaviors of the three phthalocyanine (Pc) derivatives in water. The inclusion of the Cu2+ cation in the Pc structure reinforces the appearance of two axial water molecules and second-shell water molecules in the solvent structure, whereas the presence of SO3− anions implies a well defined hydration shell of about eight water molecules around them making the macrocycle soluble in water. Debye– Waller factors for axial water molecules have been obtained in order to examine the potential sensitivity of the extended x-ray absorption fine structure technique to detect the axial water molecules.