LAUSR

Abstract Phthalocyanines (Pcs) and their derivatives have attracted a lot of attention because of their both biological importance and technological applications. The properties of Pcs can be tuned by replacing the central atom, by modifying the periphery of phthalocyanine ring, and by changing the meso-atoms. One more promising pathway for modifying Pcs and their derivatives can be the core-modification, or substitution of the core isoindole nitrogen(s) by other elements. Motivated by the results obtained for some core-modified porphyrins, we investigated computationally complete core-modification of regular Zn phthalocyanine (ZnPc) with P and S. We performed density functional theory studies of the structures, charges, and frontier molecular orbitals of P-core-modified and S-core-modified ZnPcs, ZnPc(P)4 and ZnPc(S)4, using both B3LYP and two dispersion-corrected functionals. Also, we studied computationally formation of complexes between the fullerene C60 and ZnPc(P)4 and ZnPc(S)4. Both ZnPc(P)4 and ZnPc(S)4 show strong bowl-like distortions similar to the results obtained earlier for ZnP(P)4 and ZnP(S)4. The size of the “bowl” cavity of the both core-modified Pcs is essentially the same, showing no dependence on the core-modifying element. For ZnPc(S)4, the HOMO is quite different from those of ZnPc and ZnPc(P)4. When the fullerene C60 forms complexes with the ZnPc(P)4 and ZnPc(S)4 species in the gas phase, it is located relatively far (4.30–5.72 Å) from the one of the P-centers and from the Zn-center of ZnPc(P)4, whereas with ZnPc(S)4 C60 forms relatively short bonds with the Zn-center, varying from ca. 2.0 to ca. 3.0 Å. The very strong deformations of both the ZnPc(P)4 and ZnPc(S)4 structures are observed. The calculated binding energy at the B3LYP/6-31G* level for the C60-ZnPc(P)4 complex is quite low, 1.2 kcal/mol, which agrees with the quite long distances fullerene - ZnPc(P)4, whereas it is noticeably larger, 13.6 kcal/mol, for the C60-ZnPc(S)4 complex which again agrees with the structural features of this complex. The binding energies of the complexes optimized using the dispersion-corrected functionals, CAM-B3LYP and wB97XD, are significantly larger, varying from ca. 14 till 52 kcal/mol which corresponds with the shorter distances between the fullerene and ZnPc(X)4 species.