Intermolecular Interactions in Fluorinated Tetraarylporphyrins: An Experimental and Theoretical Study

Crystallographic studies of the fluorinated tetraarylporphyrin 5,10,15,20-tetrakis(2,3,5,6-tetrafluoro-N,N-dimethyl-4-anilinyl)porphyrin and its metal complexes [MTF4DMAP; M = 2H center dot 2H2O, 1; NiII center dot THF, 2; CuII center dot 5H2O, 3; and ZnII center dot(THF)2, 4; THF = tetrahydrofuran] are reported. To analyse the weak intermolecular interactions, we have used a combination of energy decomposition analysis and Hirshfeld surface analysis, which allowed us to elucidate the nature of various close contacts. The energy decomposition analysis shows that dispersive interactions involving fluorine atoms significantly contribute to the stabilizing intermolecular interactions. Cooperative weak interactions such as C-F center dot center dot center dot H/C/F, C-H center dot center dot center dot and H center dot center dot center dot H are responsible for the formation and stabilization of the supramolecular self assemblies.