A Covalently Linked Dyad Based on Zinc Phthalocyanine and Methylpheophorbide a: Synthetic and Physicochemical Study

Irina O. Balashova,^a Alexander Yu. Tolbin,^a Pavel A. Tarakanov,^a Alexei R. Krot,^b Kseniya V. Fedorova,^b Irina A. Sergeeva,^b Stanislav A. Trashin,^a,c Karolien De Wael,^c Victor E. Pushkarev,^a@ Mikhail O. Koifman,^d and Gelii V. Ponomarev^e

^aInstitute of Physiologically Active Compounds, Russian Academy of Sciences, 142432 Chernogolovka, Moscow Region, Russia

^bDepartment of Physics, M.V. Lomonosov Moscow State University, 119991 Moscow, Russia

^cAXES Research Group, Department of Chemistry, University of Antwerp, 2020 Antwerpen, Belgium

^dIvanovo State University of Chemistry and Technology, Research Institute of Macroheterocycles, 153000 Ivanovo, Russia

^eV.N. Orekhovich Institute of Biomedical Chemistry, 119121 Moscow, Russia

^@Corresponding author E-mail: pushkarev@ipac.ac.ru

DOI: 10.6060/mhc210338p

Macroheterocycles 2021 14(1) 40-50

Dedicated to the memory of Professor Larisa G. Tomilova

The first covalently linked conjugate of metal phthalocyaninate and chlorin e₆ derivative has been obtained by transesterification of α-ketomethyl ester in methylpheophorbide a with zinc(II) 2‑(2‑hydroxymethylbenzyloxy)-9(10),16(17),23(24)-tri-tert-butylphthalocyaninate under mild conditions. The dyad exhibits a panchromatic nature revealing both the phthalocyanine and pheophorbide derived bands in the UV-Vis absorption spectrum. The ¹H NMR spectroscopy data combined with theoretical calculations indicate the presence of spatial intramolecular interactions between the phthalocyanine, pheophorbide and spacer fragments of the dyad allowing to forecast its enhanced nonlinear optical properties, as well as the characteristic energy transfer from the excited pheophorbide subunit to the phthalocyanine core. Indeed, when excited in the UV-Vis range, the conjugate shows red fluorescence with the spectral maximum at 686 nm, which is close to the one of the initial zinc phthalocyaninate. Furthermore, the dyad effectively generates singlet oxygen and, in the presence of polyvinylpyrrolidone (PVP) as biocompatible solubilizer, forms stable micellar saline solutions with the particles ranged in size between 40 and 100 nm. These nanoparticles represent promising third-generation photosensitizing systems for application in theranostics.

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A Covalently Linked Dyad Based on Zinc Phthalocyanine and Methylpheophorbide a: Synthetic and Physicochemical Study

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