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Design and synthesis of novel photosensitizer architectures is a key step toward new multifunctional molecular materials. Photoactive Janus-type molecules provide interesting building blocks for such systems by presenting two well-defined chemical functionalities that can be utilized orthogonally. Herein a multifunctional phthalocyanine is reported, bearing a bulky and positively charged moiety that hinders their aggregation while providing the ability to adhere on DNA origami nanostructures via reversible electrostatic interactions. On the other hand, triethylene glycol moieties render a water-soluble and chemically inert corona that can stabilize the structures. This approach provides insight into the molecular design and synthesis of Janus-type sensitizers that can be combined with biomolecules, rendering optically active biohybrids.

Newly metallo-phthalocyanines substituted MPc1 of zinc, copper, and palladium, bearing 3-((2,6-di(pyridin-3-yl)-phenoxy) substituent at [Formula: see text]-position (non-peripheral) were synthesized and characterized by common spectroscopic methods such as 1H-NMR, IR-FTR, MS, UV-Visible and florescence emission. Flowing several synthetic routes, the yield was increased in the series of metals: from CuPc1, PdPc1, to ZnPc1 and from ZnPc1, to ZnPc2, to ZnPc3, compared with their analogies in the literature. Afterwards, the effect of changing metals and substituents’ positions increased the Q-band value and florescence emission from PdPc1 to CuPc1 to ZnPc1 and from ZnPc2 ([Formula: see text]-position) to ZnPc3 (octa-position), to ZnPc1([Formula: see text]-position) and from cationic phthalocyanines ZnPc 2Me to ZnPc 3Me to ZnPc 1Me. The study of aggregation tendance in DMSO was examined in different concentrations to confirm that there was no aggregation appearance.

Photodynamic therapy combines light, molecular oxygen and a PS for the production of reactive oxygen species (ROS), such as singlet oxygen (1O2) and free radicals, leading to oxidative stress and eventual cell death. Phthalocyanines (Pcs) fulfil many of the requirements to be applied as photosensitizers for singlet oxygen generation.1,2 However, a major drawback of these compounds is their low solubility in physiological media. Functionalization of the macrocycle at the peripheral and/or axial positions with appropriate hydrophilic functions provides compounds with an enhanced solubility in water. In this respect, several strategies have been adopted to increase the hydrophilicity of Pcs and make them more bio-compatible, like their functionalization with charged groups,3 aminoacids4 or carbohydrates.5 The introduction of such entities at Pc axial positions reduces the aggregation of the macrocycles in solution, thus improving their 1O2 generation efficiency. For recent work of our group, see reference 1 and articles cited therein. 1Almeida-Marrero V, van de Winckel E, Anaya-Plaza E, Torres T and de la Escosura A. Chem. Soc. Rev., 2018; 47: 7369-7400. 2Dąbrowski JM, Pucelik B, Regiel-Futyra A, Brindell M, Kyzioł A, Stochel G, Macyk W and Arnaut LG. Coord. Chem. Rev., 2016; 325: 67-101. 3Setaro F, Ruiz-González R, Nonell S, Hahn U and Torres T. J. Inorg. Biochem., 2014; 136: 170-176. 4Chen Z, Zhou S, Chen J, Deng Y, Luo Z, Chen H, Hamblin MR, and Huang M. ChemMedChem, 2010; 5: 890-898. 5Alvarez-Mico X, Calvete MJF, Hanack M, Ziegler T. Tetrahedron Lett., 2006; 47: 3283-3286.