This work is devoted to a multiscale computational study of metal complexes with SalEn-type Schiff bases aggregation phenomena, which play an important role in the synthesis of polymeric conductive films on electrode surfaces and strongly affect the structure of the resulting polymers. The choice of six relatively simple [Ni(Schiff)] complexes considered in this study was based on the expected steric and electronic effects of substituents and was intended to reflect the variety of molecular-level properties. Molecular dynamics simulations were used to study the adsorption layers formation. A link between the possible dimer structures and the properties of films adsorbed at inert surfaces was established, and the primary types of possible structures for noncovalently bound dimeric complexes were identified. Quantum chemical DFT calculations were employed to investigate bimolecular aggregates. The existence of stable bimolecular units of [Ni(Schiff)] complexes is mainly determined by dispersion interactions, while their structure is predominantly governed by electrostatic interactions. The existence of the most favorable plane-parallel structure type was confirmed for all the complexes considered in this study. Along with the formation of hydrogen bonds, d-d and π-d orbital interactions are possible for some of the complexes, though these types of bonding appear to have a relatively small effect on the orientation of molecules in dimeric units.
Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films