Platinum-blues synthesis

Shi et al. [70] were the first to demonstrate the use of an air and moisture stable ionic liquid, [C4mim][PF,s], for the electrochemical synthesis of poly(thiophene), grown onto a platinum working electrode by potentiodynamic, constant potential or constant current techniques. The use of growth potentials between 1.7 and 1.9 V (vs. Ag/AgCl) reportedly gave smooth, blue-green electroactive films, whereas potentials above 2 V resulted in film destruction by overoxidation. 

The insolubilities of phthalocyanines made their analysis difficult and it took some time before a satisfactory structure was elucidated. Initial work was undertaken by the Linstead group at Imperial College in the 1930s that culminated in a series of six back to back papers published in 1934 [14], It was also Linstead who named the compounds in recognition of their synthesis from phthalic anhydride and similarity to the blue cyanine dyes. Definitive characterization of the nickel, platinum and copper phthalocyanine complexes, together with the metal-free compound, was revealed in 1935 following the publication of their X-ray structures by Robertson [15] the copper and metal-free compounds are illustrated in Fig. 7.5. 

ROMP copolymers were also explored to disperse a platinum chromophore in a solvent in which the parent chromophore was insoluble. Slugovc et al. [75] reported the synthesis of amphiphilic triblock random copolymers containing a blue fluorescent host and a red phosphorescent guest. Deep red phosphorescence, stemming from the platinum complex used as guest component, was observed with a large Stokes shift of about 260 nm. Moreover, considerable phosphorescent quantum yields were demonstrated thanks to a suppression of the self-aggregation of the platinum complex. In a further work, the same... 

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