Optical and Supramolecular Properties of Cyclometalated Palladium Nanostructures with Tumor Targeting Properties in Living Mice: A Quantum Mechanics Interpretation.

Abstract The recent discovery that metallophilic interactions between cyclometalated palladium supramolecular nanostructures – with efficient tumour accumulation rate in a skin melanoma model – maintain excellent photodynamic properties even in a hypoxic microenvironment has inspired the present study focused on the theoretical predictions of optical properties of the bis‐cyclometalated palladium compound in different contexts. More specifically, structural and UV/Vis absorption properties of both monomeric and dimeric forms of this anticancer drug are well reproduced with a Time‐Dependent Density Functional Theoretical (TD‐DFT) approach based on Exchange–Correlation (XC) hybrid functionals in conjunction with conductor‐like and polarization solvation effects. A further novelty is represented by a fine investigation of the supramolecular interactions between the different subunits of the drug via dispersion force correction and Quantum Theory of Atoms in Molecules (QTAIM). This contribution while supporting the photoexcitation properties derived in laboratory following the self‐assembly of monomeric units when passing from dimethyl sulfoxide (DMSO) to a H 2 O/DMSO mixture at 298 K, shed some light on the nature of the chemical interactions modulating the formation of nano‐size aggregates.