Yudai Ichikawa, Yui Sakuma, Kanami Sugiyama, Satoshi Takahashi, Tomomi Shimazaki, Masahiro Higashi, Shuichi Hiraoka, Hirofumi Sato, Masanori Tachikawa
In order to elucidate the mechanism of self-assembly of a caged dinuclear palladium complex [Pd2L4]4+, three reaction pathways were examined with density functional theory. We found that, among several competitive assembly paths, dynamical selection among them could occur due to the consumption of a specific chemical species. The insufficient supply of the ligand can narrow the reaction flow along the related path and, in some cases, force a bypass to a different path. Coarse-grained modelling was also proposed to analyse assembly processes and to extract the physicochemical background. We found that the solute-solvent electrostatic interaction, ΔGes, stabilises the dinuclear complexes, significantly reducing the repulsion between the palladium ions. The cavitation energy ΔGcav, primarily related to the overlap of excluded volumes of the ligands, lowers the association activation free energy.