Water-Involved Hydrogen Bonds in Dimeric Supramolecular Structures of Magnesium and Zinc Phthalocyaninato Complexes

[Image: see text] Two dimeric supramolecular structures {MgPc(H(2)O)·4-methylmorpholine}(2)—(1) and {ZnPc(H(2)O)·4-methylmorpholine}(2)—(2) formed from two molecules of magnesium and zinc aquaphthalocyanines in 4-methylmorpholine solution were revealed by single-crystal X-ray diffraction. Coordinated H(2)O molecules to the metal center of respective Mg or Zn phthalocyanines oriented face-to-face to form two hydrogen bonds, one of them connecting via O–H···N-azamethine atom to form a dimeric structure in the crystals with ring-to-ring distances of 3.412(3) Å in 1 and 3.403(5) Å in 2, whereas the second hydrogen bonds link the solvent 4-methylpholine molecules to form supramolecular dimeric {MgPc(H(2)O)·4-methylmorpholine}(2)—(1) and {ZnPc(H(2)O)·4-methylmorpholine}(2)—(2) structures. The interaction of the metal center of MgPc or ZnPc with O atom of the water molecule results its displacement of ∼0.5 Å from the N(4)-isonodole plane of the phthalocyaninate(2-) macrocycle that adopts a saucer-shape form. To better understand the interactions leading to the existence of the dimeric structures in the crystals, theoretical calculations of dimer stabilization energy composed of two monomers (MgPcH(2)O and ZnPcH(2)O), as well as three-dimensional molecular electrostatic potentials, have been performed using the density functional theoretical method. The calculated absorption spectra of both supramolecular monomers and dimers were compared with the experimental ones in 4-methylmorpholine solution. The water axial ligation of MgPc and ZnPc and the formation of the monomeric and dimeric supramolecular structures only slightly change the energy gap between highest occupied molecular orbital and lowest unoccupied molecular orbital levels that is compared with those of the parent MgPc and ZnPc pigments.