Since J. Monteath Robertson reported the first single-crystal structures of phthalocyanine complexes in 1935, many other structures have been solved. However, most of the original literature focuses on the molecular description of these complexes and very little is known about their solid-state arrangements. Until today, the single-crystal structures of phthalocyanines and related macrocycles have not been reviewed in detail.
Since many solid-state properties critically depend on the solid-state structures, a comparative review could improve our understanding of the solid-state arrangements of phthalocyanines and give further insight into the molecular engineering of aromatic macrocyclic compounds. This review uses the concept of molecular shape to classify 200 single-crystal structures of phthalocyanines and naphthalocyanines into two main groups.
The first group is characterized by similar shaped molecular sides, whereas the second group has two distinguishable sides. Both types of complex show different patterns of solid-state arrangement.
Some topics of phthalocyanine structural research, for example, the location of the inner hydrogens in metal-free phthalocyanine, the coordination chemistry of the central metal in metallophthalocyanines, the staggering angle in bisphthalocyanines, the deformation of solid-state molecular structures, as well as linear and slipped-stacking, herringbone and brickstone arrangements, which play a crucial role in the efficiency of phthalocyanine photoreceptors, are treated in details.
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