Porphyrinoids dimerization

The aforementioned representative examples of chirogenic supramolecular systems based on monomeric porphyrinoids clearly demonstrate their vital importance and wide applicability in various fields, while many aspects of the operating mechanisms and especially chiroptical properties have yet to be comprehensively investigated and well understood. However, in many cases just a monomeric porphyrin cannot function properly without the synergetic assistance of another porphyrin unit (or several porphyrins) that give rise to chirogenic supramolecular assemblies built upon the dimeric/oligomeric porphyrinoids, which will be discussed in subsequent sections. 

Chirogenic supramolecular systems based on dimeric/oligomeric porphyrinoids can also be classified according to their complexity and structural features. First, the assemblies consisting of two or more monomeric porphyrins fixed in an asymmetrical fashion by chiral bridges via supramolecular binding will be examined. 

Supramolecular systems on the basis of dimeric and oligomeric porphyrinoids are varied depending upon the chirality of the supramolecular counterparts, type of the covalent linkage, and number of the porphyrin subunits. Firstly, we shall examine examples of the assemblies consisting of achiral and racemic bis-porphyrinoid hosts and chiral guests. 

The supramolecular assemblies involving aggregated porphyrinoids similarly to other types of previously discussed systems could be reasonably divided into different categories on the basis of achiral, chiral monomeric, and dimeric porphyrinoids. Again, the simplest monomeric achiral porphyrinoids will be presented first. 

While self-assembled and aggregated chirogenic systems are mainly based on monomeric porphyrinoids, a further increase of the pigment multiplicity, despite raising the overall complexity of supramolecular structures, may lead to novel functional properties and new applications. Therefore, in the last section we shall show a few examples of self-assembled and aggregated systems constructed from dimeric and oligomeric porphyrins. 

Since this class of supramolecular assemblies is represented by a small number of examples due to the enhanced structural intricacy and synthetic complexity, we shall present both chiral and achiral dimeric/oligomeric porphyrinoid-based systems in one section. 

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