Ligand release from IR700, a silicon phthalocyanine dye used in near-infrared (NIR) photoimmunotherapy, initiates cancer cell death after NIR absorption, although its photochemical mechanism has remained unclear. This theoretical study reveals that the direct Si-ligand dissociation by NIR light is difficult to activate because of the high dissociation energy even in excited states, i. e., >1.30 eV. Instead, irradiation generates the IR700 radical anion, leading to acid-base reactions with nearby water molecules (i. e., calculated pKb for the radical anion is 7.7) to produce hydrophobic ligand-released dyes. This suggests two possibilities: (1) water molecules participate in ligand release and (2) light is not required for Si-ligand dissociation as formation of the IR700 radical anion is sufficient. Experimental evidence confirmed possibility (1) by using 18 O-labeled water as the solvent, while (2) is supported by the pH dependence of ligand exchange, providing a complete description of the Si-ligand bond dissociation mechanism.
Keywords: bond dissociation; cancer photoimmunotherapy; density functional calculation; near-infrared dyes; radical anions; silicon phthalocyanine.
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.