| Full text | |
| Author(s): |
Duarte Lopez, Alfredo Henrique
[1]
;
Caramori, Giovanni Finoto
[1]
;
Coimbra, Daniel Fernando
[1]
;
Tame Parreira, Renato Luis
[2]
;
da Silva, Eder Henrique
[2]
Total Authors: 5
|
| Affiliation: | [1] Univ Fed Santa Catarina, Dept Chem, BR-88040900 Florianopolis, SC - Brazil
[2] Univ Franca UNIFRAN, Nucleo Pesquisas Ciencias Exatas & Tecnol, BR-14404600 Franca - Brazil
Total Affiliations: 2
|
| Document type: | Journal article |
| Source: | ChemPhysChem; v. 14, n. 17, p. 3994-4001, DEC 2 2013. |
| Web of Science Citations: | 8 |
| Abstract | |
`Systems that are connected through multiple hydrogen bonds are the cornerstone of molecular recognition processes in biology, and they are increasingly being employed in supramolecular chemistry, specifically in molecular self-assembly processes. For this reason, the effects of different substituents (NO2, CN, F, Cl, Br, OCH3 and NH2) on the electronic structure, and consequently on the magnitude of hydrogen bonds in triple AAA-DDD arrays (A=acceptor, D=donor) were evaluated in the light of topological {[}electron localization function (ELF) and quantum theory of atoms in molecules (QTAIM)], energetic {[}Su-Li energy-decomposition analysis (EDA) and natural bond orbital analysis (NBO)], and geometrical analysis. The results based on local H-bond descriptors (geometries, QTAIM, ELF, and NBO) indicate that substitutions with electron-withdrawing groups on the AAA module tend to strengthen, whereas electron-donating substituents tend to weaken the covalent character of the AAA-DDD intermolecular H-bonds, and also indicate that the magnitude of the effect is dependent on the position of substitution. In contrast, Su-Li EDA results show an opposite behavior when compared to local H-bond descriptors, indicating that electron-donating substituents tend to increase the magnitude of H-bonds in AAA-DDD arrays, and thus suggesting that the use of local H-bond descriptors describes the nature of H bonds only partially, not providing enough insight about the strength of such H bonds. (AU) | |
| FAPESP's process: | 12/22440-0 - Computational study of bonding and chemical interactions in complexes formed by oxocarbons, pseudo-oxocarbons, and squaraines with spectroscopic, electronic and optical properties |
| Grantee: | Eder Henrique da Silva |
| Support Opportunities: | Scholarships in Brazil - Master |
| FAPESP's process: | 11/07623-8 - The use of quantum-mechanical methods to study the bonds and chemical interactions in self-organizing systems with applications in catalysis, medicinal chemistry, electrochromism, energy storage and conversion |
| Grantee: | Renato Luis Tame Parreira |
| Support Opportunities: | Research Grants - Young Investigators Grants |