Nature of the dative Nitrogen-Coinage metal bond in molecular Motors. Evaluation of NHC-M pyrazine bond (M = Cu, Ag, Au) from relativistic DFT
Autor
Olea-Ulloa, Carolina
Guajardo-Maturana, Raul
Rodríguez-Kessler, Peter L.
Muñoz-Castro, Alvaro
Resumen
The use of different N-heterocyclic carbene (NHC) coordinated to coinage metals are useful caps for generating mechanical bonds towards donor-nitrogen fragments, leading to the characterization of efficient molecular motors. Here, we account for the nature of the formation of mechanical bonds on [(NHC-M)2pyz]2+ (M = Cu, Ag, Au; pyz = pyrazine) complexes. The NHC-M pyrazine interaction is of main electrostatic character given by the Lewis acidic σ-hole characteristics of the NHC-M caps, and the Lewis basic features of the aromatic pyrazine ring, accounting for the 69.9 %, 71.8 %, and 68.8 %, for Cu, Ag, and Au species, respectively. The rotational barrier is calculated at 10.2, 8.6, and 6.0 kcal mol−1, respectively, which is given by the variation of the NHC-M pyrazine interaction, and structural arrangements, accounting for 54.0/46.0 %, 59.3/40.7 %, and, 79.8/20.2 %, for Cu, Ag, and Au, respectively. Hence, the rotational barrier for the gold counterpart is less affected by structural factors. Relativistic effects on the N-coinage metal bond interaction are crucial for the account of the experimentally observed rotational barrier. Thus, the theoretical evaluation of mechanical bonds allows to gain further insights into the fundamental nature of the interaction and how structural factors affect the formation of molecular motors relevant to guide design and synthetic efforts.
Colecciones
Ítems relacionados
Mostrando ítems relacionados por Título, autor o materia.
-
Article
Coinage-metal pillarplexes hosts. Insights into host-guest interaction nature and luminescence quenching effects (2021)
Rojas-Poblete, Macarena; Rodríguez-Kessler, P. L.; Guajardo-Maturana, Raúl; Munõz-Castro, Álvaro (Royal Society of Chemistry, 2021-08-14)Host-guest chemistry is a relevant issue in materials science, which encourages further development of versatile host structures. Here the particular features of coinage-metal pillarplexes are evaluated towards formation ... -
Article
Nature of hydride and halide encapsulation in Ag8cages: insights from the structure and interaction energy of [Ag8(X){S2P(OiPr)2}6]+(X = H−, F−, Cl−, Br−, I−) from relativistic DFT calculations (2022)
Guajardo-Maturana, Raúl; Ortolan, Alexandre Osmar; Rodríguez-Kessler, P. L.; Caramori, Giovanni Finoto; Parreira, R. L.T.; Muñoz-Castro, Álvaro (Royal Society of Chemistry, 2022-01-07)Unraveling the different contributing terms to an efficient anion encapsulation is a relevant issue for further understanding of the underlying factors governing the formation of endohedral species. Herein, we explore the ... -
Article
On the 13C-NMR chemical shift anisotropy patterns and aromatic character in strained fullerenes: Computational analysis of D6h/D2d-C36 fullerene (2020)
Guajardo‐Maturana, Raul; Rodríguez-Kessler, Peter L.; MacLeod‐Carey, Desmond; Muñoz‐Castro, Álvaro (John Wiley and Sons Inc., 2020-09-05)The NMR characterization of small C36 hollow fullerene exposes a stable cage with structural features based on its strained curved π-surface in a D6h-symmetry. Our results indicate that planar-like aromatic properties of ...