Phthalocyanine-Based Polymers and Dendrimers

Especially attractive is the route developed by Hanack and co-workers to obtain main-chain-type polymers based on Pcs, which relies on the connection of the 

Another example of a Pc-based 1-D polymer is that reported by Armstrong and co-workers [158], They prepared a Pc with eight styrene-type polymerizable sites at the end of the peripheral substituents. This molecule forms highly ordered, rod-like aggregates at the air-water interface that can be transferred onto solid supports. Irradiation of the thin films affords polymerization between the olefin moieties of adjacent molecules by photostimulated [2 + 2] cycloaddition. The rod-like Pc macromolecules were conveniently studied by matrix-assisted laser desorp-tion/ionization (MALDI-TOF) spectrometry and atomic force microscopy (ATM), the latter showing rods with lengths up to 290 nm. 

As mentioned above, Pcs can be incorporated as side groups of a main polymeric chain. Two routes can be followed to achieve this goal. One of them involves the polymerization (or copolymerization) of unsymmetrically substituted Pcs, i.e., holding reactive sites at one of the isoindole subunits. The second one requires the preparation of a polymer with side functional groups that can react in a further step with an appropriately functionalized Pc. 

Recent examples of the first route have been described by Kobayashi and coworkers, who reported the synthesis and characterization of polymeric Pcs obtained through the olefin metathesis polymerization of terminal olefin groups in the side chains of unsymmetrical Pc monomers [159], X-ray analysis of the solid material indicates that the Pcs are ordered in stacks. 

The incorporation of pendant Pcs to a polymeric backbone via the grafting of a suitable Pc molecule to a preformed polymer containing appropriate functional groups has been accomplished by Chen and co-workers [163], These authors exploited the axial reactivity of some metalloPcs (namely, In(III)Pcs) to prepare an In(III)Pc-polystyrene copolymer. The most remarkable feature of this material is that cofacial association between the macrocycles is fully prevented. For some applications of the Pcs, such as optical limiting or photodynamic therapy (PDT), aggregation should be avoided because it produces the quenching of the excited-states. 

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