Nanotheranostic tailor‐made carriers are potent platforms for the treatment of cancer that propound a number of advantages over conventional agents for photodynamic therapy (PDT). Herein, four new heavy atom free amphiphilic glucose‐BODIPY‐fullerene dyads (14–17) endowed with carbohydrate units in the styryl units, which can also form nanomicelles (14–17NM) with Tween 80 for PDT are reported. Glucose‐BODIPY‐fullerene systems (14–17) and related nanomicelles (14‐17NM) have been prepared to emcee efficient singlet oxygen generation upon light irradiation. In vitro anti‐tumor effects of the compounds 14–17 and 14–17NM in the presence of light and in darkness have been investigated with K562 human chronic myelogenous leukemia suspension cells. Anti‐tumor toxicity upon light irradiation was due to the formation of singlet oxygen and reactive oxygen species (ROS). This study may provide an accomplished example of efficient PDT applications based on nanovehicles fabricated with universal spin converter, fullerene, light harvesting unit, BODIPY dyes conjugated with targeting units to fight against cancer.

Nucleophilic substitution reactions of N(3)P(3)Cl(4)[NH(CH(2))(3)NMe] (1) and N(3)P(3)Cl(4)[NH(CH(2))(3)O] (2) with mono-functional alcohols (methanol, 2,2,2-trifluoroethanol, phenol) and a secondary amine (pyrrolidine) were used to investigate the relationship between the incoming nucleophile and the proportions of products with substituents that are cis or trans to the spiro NH moiety. The reaction products were characterized by elemental analysis, mass spectrometry, (1)H and (31)P NMR spectroscopy and the configurational isomers by X-ray crystallography. Six products have been characterised with the substituent cis to the spiro NH group for the alcohol (methanol, phenol) and pyrrolidine derivatives of both compounds 1 and 2, compared to just one derivative with the substituent trans to the spiro NH group, that for the pyrrolidine derivative of compound 2. For each reaction the relative proportions of cis and trans isomers were determined by (31)P NMR measurements of the reaction mixtures. It was found that the reactions of compound 1 with all three alcohols and of compound 2 with methanol lead to exclusive formation of isomers with the substituent cis to the NH moiety, whereas all other reactions lead to mixtures of cis and trans isomers in different ratios under standard reaction conditions. However, when crown ether is included in the reaction medium for the reactions of compound 2 with both 2,2,2-trifluoroethanol and phenol, it is found that only cis isomers are formed. All these results are rationalised in terms of the competition between at least two effects; the cis-directing effect by hydrogen bonding of the incoming nucleophile to the spiro N-H group already present on the cyclophophazene ring and the cis-directing effect of the sodium cation coordinating to the oxygen lone pairs of the P-O moiety of the spiro ring.

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