TY - JOUR

T1 - Assembly of [Ni(Schiff)] Films on an Inert Surface

T2 - A Multiscale Computational Study

AU - Hrom, Siarhei

AU - Sizov, Vladimir V.

AU - Levin, Oleg V.

AU - Laaksonen, Aatto

N1 - Funding Information: This work was supported by the Russian Science Foundation (Grant Number 19-19-00175). A.L. thanks for partial support by a grant from the Ministry of Research and Innovation, CNCS - UEFISCDI, Project Number PN-III-P4-ID-PCCF-2016-0050, within PNCDI III. The access to the facilities of the Computational Resource Center (Science Park, St. Petersburg State University) is gratefully acknowledged. Publisher Copyright: © 2021 American Chemical Society. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/2/11

Y1 - 2021/2/11

N2 - 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.

AB - 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.

KW - SCHIFF-BASE COMPLEXES

KW - NICKEL-COMPLEXES

KW - POLYMER-FILMS

KW - MOLECULAR-DYNAMICS

KW - CARBON MATERIALS

KW - METAL-COMPLEXES

KW - ENERGY-STORAGE

KW - DENSITY

KW - ELECTROPOLYMERIZATION

KW - METALLOPOLYMERS

UR - http://www.scopus.com/inward/record.url?scp=85100669292&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/385fd582-2bdd-3e67-9948-cd00f5902145/

U2 - 10.1021/acs.jpcc.0c09085

DO - 10.1021/acs.jpcc.0c09085

M3 - Article

AN - SCOPUS:85100669292

VL - 125

SP - 2926

EP - 2937

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 5

ER -