Chem. Eur. J. 14, 1342-1350 (2008)

DOI: 10.1002/chem.200701542

Synthesis, Characterization, Molecular Structure and Theoretical Studies of Axially Fluoro-Substituted Subazaporphyrins

A new and general synthetic method for the preparation of fluoro-substituted subazaporphyrins is reported that involves the treatment of the corresponding chloro- or aryloxy-substituted subazaporphyrins (SubAPs) with BF3⋅OEt2. The strategy has been applied to both subphthalocyanines (SubPcs) and subporphyrazines (SubPzs). The yields were high for the latter, although low yields were obtained for the benzo derivatives. In contrast to the corresponding chloro derivatives, fluorosubazaporphyrins are quite robust towards hydrolysis. All of the new compounds were characterized by several spectroscopic techniques, which included 1H, 13C, 19F, 15N, and 11B NMR spectroscopy, IR spectroscopy, UV/Vis spectrophotometry, and mass spectrometry (both high and low resolution). In addition, DFT calculations provided theoretical NMR spectroscopy values that are in good agreement with the experimental ones. The high dipole moments exhibited by the fluorosubazaporphyrins as a result of the presence of a fluorine atom in an axial position are responsible for the spontaneous and singular supramolecular aggregation of the macrocycles in the crystalline state. The molecular and crystal structures of two one-dimensional fluorine SubAPs, namely, a SubPc and a SubPz, are discussed. Molecules of the same class stack in alternating configurations along the c axis, which gives rise to columns that contain large numbers of monomers. SubPz 3 c forms aggregates with the macrocycles arranged in a parallel fashion with the BF bonds perfectly aligned within a column, whereas with SubPc 3 b the neighboring columns cause a commensurate sinusoidal distortion along the columns in the c direction, which prevents the alignment of the BF bonds. However, the most remarkable feature, common to both crystalline architectures, is the extremely short and unusual intermolecular F⋅⋅⋅N distances of the contiguous molecules, which are shorter than the sum of the corresponding van der Waals radii. Theoretical calculations have shown that these short distances can be explained by the existence of a cooperativity effect as the number of monomers included in the cluster increases.