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. 2019 Feb 19;4(2):3673-3683.
doi: 10.1021/acsomega.8b03055. eCollection 2019 Feb 28.

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

Jan Janczak  1
Affiliations

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

Jan Janczak. ACS Omega. .

Abstract

Two dimeric supramolecular structures {MgPc(H2O)·4-methylmorpholine}2-(1) and {ZnPc(H2O)·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 H2O 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(H2O)·4-methylmorpholine}2-(1) and {ZnPc(H2O)·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 N4-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 (MgPcH2O and ZnPcH2O), 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.

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Conflict of interest statement

The author declares no competing financial interest.

Figures

Figure 1
Figure 1
Calculated 3D MESP is mapped onto the total electron density isosurface (0.008 e Å–3) for MgPc (a), ZnPc (b), H2O (c), and 4-methylmorpholine (d). The color code of MESP is in the range of −0.05 (red) to 0.05 e Å–1 (blue).
Figure 2
Figure 2
3D MESP for MgPc(H2O) (a) and ZnPc(H2O) (b). The color code as in Figure 1.
Figure 3
Figure 3
3D MESP for (MgPcH2O)2 (a) and (ZnPcH2O)2 (b). The color code as in Figure 1.
Figure 4
Figure 4
View of the molecular structure of the dimeric structure of MgPc(H2O)·4-methylmorpholine (a) and ZnPc(H2O)·4-methylmorpholine (b).
Figure 5
Figure 5
Packing view of dimeric structure of MgPc(H2O)·4-methylmorpholine (a) and ZnPc(H2O)·4-methylmorpholine (b).
Figure 6
Figure 6
HS and 2D fingerprint plots for (a) Mg- and (b) Zn-monomers.
Figure 7
Figure 7
HS and 2D fingerprint plots for (a) Mg- and (b) Zn-dimers.
Figure 8
Figure 8
View of the DFT optimized dimers of (MgPcH2O)2 (a), (ZnPcH2O)2 (b), and (BePcH2O)2 (c).
Figure 9
Figure 9
UV–vis spectra of 1 (a) and 2 (b) in 4-methylmorpholine solution.
Figure 10
Figure 10
Partial molecular energy diagram, HOMO and LUMO frontier orbitals, and the calculated absorption spectra for the MgPc(H2O) and ZnPc(H2O) complexes.
Figure 11
Figure 11
Partial molecular energy diagram, HOMO and LUMO frontier orbitals, and the calculated absorption spectra for the (MgPcH2O)2 and (ZnPcH2O)2 dimers.
See this image and copyright information in PMC

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