A QCT View of the Interplay between Hydrogen Bonds and Aromaticity in Small CHON Derivatives
Abstract
:1. Introduction
2. Theoretical Framework
2.1. Real Space Wavefunction Analyses
2.2. Aromaticity
3. Computational Details
4. Results and Discussion
4.1. General Energetic Changes Induced by HB Formation
4.2. Quantum Chemical Topology Analyses
4.3. Perturbation of the Aromaticity of the π Skeleton
4.4. The Peculiar Case of the AZH (DCR) Dimer
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
Sample Availability
References
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System | System | ||||
---|---|---|---|---|---|
2HP (ACR) | 5.06 | 3.01 | 2HP (DCR) | −7.11 | −7.03 |
NCO (ACR) | 0.00 | 0.00 | NCO (DCR) | 0.00 | 0.00 |
AZH (ACR) | −2.82 | −3.34 | AZH (DCR) | 6.40 | 5.38 |
2AP (ACR) | 3.22 | 2.58 | 2AP (DCR) | −8.16 | −7.50 |
NCN (ACR) | 0.00 | 0.00 | NCN (DCR) | 0.00 | 0.00 |
AZA (ACR) | −10.05 | −9.58 | AZA (DCR) | 2.13 | 0.89 |
ACR | ||||
System | (D) | (H) | (A) | (C) |
2HP | −0.087 | +0.049 | −0.067 | +0.069 |
NCO | −0.085 | +0.041 | −0.072 | +0.085 |
AZH | −0.089 | +0.065 | −0.077 | +0.045 |
2AP | −0.040 | +0.070 | −0.021 | +0.019 |
NCN | −0.051 | +0.088 | −0.024 | +0.008 |
AZA | −0.061 | +0.113 | −0.063 | −0.002 |
DCR | ||||
System | (D) | (H) | (A) | (C) |
2HP | −0.070 | +0.105 | −0.024 | −0.040 |
NCO | −0.052 | +0.085 | −0.025 | −0.007 |
AZH | −0.037 | +0.064 | −0.024 | −0.011 |
2AP | −0.063 | +0.101 | −0.031 | −0.012 |
NCN | −0.051 | +0.088 | −0.024 | +0.008 |
AZA | −0.030 | +0.074 | −0.034 | −0.007 |
ACR | ||||
System | DI(D–H) | DI(D–C) | DI(C–A) | DI(H–A) |
2HP | −0.207 | +0.056 | −0.064 | +0.152 |
NCO | −0.246 | +0.100 | −0.171 | +0.197 |
AZH | −0.216 | +0.079 | −0.136 | +0.134 |
2AP | −0.151 | +0.051 | −0.034 | +0.103 |
NCN | −0.181 | +0.073 | −0.076 | +0.117 |
AZA | −0.262 | +0.131 | −0.167 | +0.165 |
DCR | ||||
System | DI(D–H) | DI(D–C) | DI(C–A) | DI(H–A) |
2HP | −0.209 | +0.065 | −0.091 | +0.132 |
NCO | −0.162 | +0.069 | −0.070 | +0.099 |
AZH | −0.103 | +0.034 | −0.043 | +0.066 |
2AP | −0.234 | +0.067 | −0.106 | +0.163 |
NCN | −0.181 | +0.073 | −0.076 | +0.117 |
AZA | −0.152 | +0.043 | −0.053 | +0.099 |
System | MCI (a.u.) | FLU (a.u.) | System | MCI (a.u.) | FLU (a.u.) | ||
---|---|---|---|---|---|---|---|
2HP (ACR) | −0.008 | +0.001 | − | 2HP (DCR) | +0.007 | −0.010 | + |
AZH (ACR) | +0.001 | −0.017 | + | AZH (DCR) | −0.001 | −0.005 | − |
2AP (ACR) | −0.004 | +0.001 | − | 2AP (DCR) | +0.007 | −0.010 | + |
AZA (ACR) | +0.004 | −0.021 | + | AZA (DCR) | −0.001 | −0.007 | − |
Isomer | (kcal/mol) | FLU (a.u.) | MCI (a.u.) |
---|---|---|---|
bent–trans | +0.48 | +0.0006 | −0.0001 |
bent–cis | 0.00 | 0.0000 | 0.0000 |
planar | +7.38 | +0.0094 | −0.0038 |
QTAIM charges | ||||
System | Q(D) | (H) | (A) | (C) |
bent–trans | −0.039 | +0.063 | −0.024 | −0.007 |
bent–cis | −0.037 | +0.064 | −0.024 | −0.011 |
planar | −0.185 | +0.127 | −0.030 | +0.065 |
Delocalisation indices | ||||
System | DI(D–H) | DI(D–C) | DI(C–A) | DI(H–A) |
bent–trans | −0.099 | +0.035 | −0.043 | +0.064 |
bent–cis | −0.103 | +0.034 | −0.043 | +0.066 |
planar | −0.169 | +0.070 | −0.068 | +0.074 |
IQA energy partition | ||||
System | ||||
bent–trans | −12.80 | −21.21 | +11.99 | −87.41 |
bent–cis | −12.87 | −18.43 | +13.47 | −88.66 |
planar | −40.98 | −121.17 | −1.07 | −106.99 |
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Gallegos, M.; Barrena-Espés, D.; Guevara-Vela, J.M.; Rocha-Rinza, T.; Pendás, Á.M. A QCT View of the Interplay between Hydrogen Bonds and Aromaticity in Small CHON Derivatives. Molecules 2022, 27, 6039. https://doi.org/10.3390/molecules27186039
Gallegos M, Barrena-Espés D, Guevara-Vela JM, Rocha-Rinza T, Pendás ÁM. A QCT View of the Interplay between Hydrogen Bonds and Aromaticity in Small CHON Derivatives. Molecules. 2022; 27(18):6039. https://doi.org/10.3390/molecules27186039
Chicago/Turabian StyleGallegos, Miguel, Daniel Barrena-Espés, José Manuel Guevara-Vela, Tomás Rocha-Rinza, and Ángel Martín Pendás. 2022. "A QCT View of the Interplay between Hydrogen Bonds and Aromaticity in Small CHON Derivatives" Molecules 27, no. 18: 6039. https://doi.org/10.3390/molecules27186039