Molecules
Centro de Química Médica, Facultad de Medicina Clínica Alemana, Universidad del Desarrollo, Santiago 7780272, Chile.
Published: March 2023
Understanding the non-covalent interactions in host-guest complexes is crucial to their stability, design and applications. Here, we use density functional theory to compare the ability of β-cyclodextrin () and heptakis(2,6-di-O-methyl)-β-cyclodextrin () to encapsulate the model guest phenol. For both macrocycles, we quantify the intramolecular interactions before and after the formation of the complex, as well as the intermolecular host-guest and host-host dimer interactions. These are individually classified as van der Waals interactions or hydrogen bonds, respectively. The results show a stronger intramolecular binding energy of , with the absolute difference being -5.53 kcal/mol relative to . Consequently, the intermolecular interactions of both cyclodextrins with phenol are affected, such that the free binding energy calculated for the /phenol complex (-5.23 kcal/mol) is ≈50% more negative than for the complex with (-2.62 kcal/mol). The latter is in excellent agreement with the experimental data (-2.69 kcal/mol), which validates the level of theory (B97-3c) used. Taken together, the methylation of increases the stability of the host-guest complex with the here studied guest phenol through stronger van der Waals interactions and hydrogen bonds. We attribute this to the disruption of the hydrogen bond network in the primary face of upon methylation, which influences the flexibility of the host toward the guest as well as the strength of the intermolecular interactions. Our work provides fundamental insights into the impact of different non-covalent interactions on host-guest stability, and we suggest that this theoretical framework can be adapted to other host-guest complexes to evaluate and quantify their non-covalent interactions.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10054123 | PMC |
http://dx.doi.org/10.3390/molecules28062625 | DOI Listing |
J Phys Chem B
January 2025
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.
Reline, which is composed of choline chloride and urea in a molar ratio of 1:2, is the first and most extensively studied deep eutectic solvent (DES). In certain applications, reline is blended with organic solvents, dimethyl sulfoxide (DMSO) in most cases, to gain improved properties. Therefore, it is crucial to have a profound understanding of the impact of DMSO on the dynamics and structures of the species in the binary mixtures.
View Article and Find Full Text PDFInorg Chem
January 2025
Department of Chemistry, University of Patras, Patras 265 04, Greece.
A new [DyBiOCl(saph)] () Werner-type cluster has been prepared, which is the first Dy/Bi polynuclear compound with no metal-metal bond and one of the very few Ln-Bi (Ln = lanthanide) heterometallic complexes reported to date. The molecular compound has been deliberately transformed to its 1-D analogue [DyBiO(N)(saph)] () via the replacement of the terminal Cl ions by end-to-end bridging N groups. The overall metallic skeleton of (and ) can be described as consisting of a diamagnetic {Bi} unit with an elongated trigonal bipyramidal topology, surrounded by a magnetic {Dy} equilateral triangle, which does not contain μ-oxo/hydroxo/alkoxo groups.
View Article and Find Full Text PDFNano Lett
January 2025
Center for High Pressure Science and Technology Advanced Research, Shanghai 201203, P. R. China.
The vibron behavior of hydrogen bears significant importance for understanding the phases of solid hydrogen under high pressure. In this work, we reveal an unusual high-pressure behavior of hydrogen confined within nanopores through a combination of experimental measurements and theoretical calculations. The nanoconfined hydrogen molecules retain an hcp lattice up to 170 GPa, yet significant deviations from the vibrational characteristics of bulk hydrogen are observed in the primary vibrons of both Raman and infrared spectra.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Department of Physics and Astronomy, University of Delaware, Newark, Delaware 19716, United States.
A dispersion-corrected density functional theory (DFT+D) method has been developed. It includes a nonhybrid dispersionless generalized gradient approximation (GGA) functional paired with a literature-parametrized dispersion function. The functional's 9 adjustable parameters were optimized using a training set of 589 benchmark interaction energies.
View Article and Find Full Text PDFOrganic cocrystals have garnered significant research attention owing to their distinctive properties and promising applications. However, challenges in molecular structure design and control of intermolecular interactions continue to impede further advancements. In this study, two novel cocrystals were successfully formed from a series of synthesized benzotriazole derivatives.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!
© LitMetric 2025. All rights reserved.