VI Uranyl Superphthalocyanine

Snbmitted by EDWARD A. CUELLAR, DJORDJE R. STOJAKOVIC, and TOBIN J. MARKS  

Template reactions2 represent an extensive and important class of chemical transformations in which a metal ion serves as the hub for the coordinative cyclization of organic ligands. The method can lead either to enhanced yields over direct cyclizations or to the formation of otherwise inaccessible macrocycles. It is in this latter context that the uranyl ion acts, as a result of its large ionic radius and propensity toward pentagonal bipyramidal coordination, to form expanded macrocycles. 

It has been known for some time that the reaction of uranyl dichloride with phthalonitrile (typical phthalocyanine condensation methodology3) yields an unusual phthalocyanine-like material 4 however, it has been only recently that this product was unambiguously shown to contain an expanded, five-subunit analogue of the phthalocyanine ligand3 (Eq. 1). 

This superphthalocyanine (SPc) complex possesses a number of interesting chemical and physicochemical properties these are discussed in detail in Reference 6. The synthesis of uranyl superphthalocyanine, U(spc)02, can be 

The combined black-purple crude product is next washed with methanol until the washings are essentially colorless. This procedure is repeated with acetone. Approximately 0.4 g of bright blue-violet crystalline product remains. This consists of a mixture of U(spc)02 and PcH2 in a mole ratio of approxi- 

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