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1. Methyl‐π Interactions. Nature of Bonding and Limits of Strength

   https://doi.org/10.1002/chem.202404712  

   Scheiner, Steve (February 2025, Chemistry – A European Journal)

   Abstract Both methyl groups and benzene rings are exceedingly common, and they lie near one another in many chemical situations. DFT calculations are used to gauge the strength of the attractive forces between them, and to better understand the phenomena that underlie this attraction. Methane and benzene are taken as the starting point, and substituents of both electron‐withdrawing and donating types are added to each. The interaction energy varies between 1.4 and 5.0 kcal/mol, depending upon the substituents placed on the two groups. The nature of the binding is analyzed via Atoms in Molecules (AIM), Natural Bond Orbital (NBO), Symmetry‐Adapted Perturbation Theory (SAPT), nuclear magnetic resonance (NMR) chemical shifts, and electron density shift diagrams. While there is a sizable electrostatic component, it is dispersion that dominates these interactions, particularly the weaker ones. As such, these interactions cannot be categorized unambiguously as either H‐bonds or tetrel bonds. 

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2. Towards and understanding of CO2 microsolvation: Microwave spectroscopy of CO2 complexes with fluoroethylenes

   Peebles, Rebecca A.; Peebles, Sean A.; Anderton, Ashley M.; Christenholz, Cori L.; Dorris, Rachel E.; Trendell, William C. (August 2017, 254th American Chemical Society National Meeting)

   The need for a deep understanding of CO2 interactions with other mols. is significant given the importance of supercrit. CO2 (s.c.-CO2) as a green solvent, and interest in design of novel materials for CO2 capture and storage. Soly. of fluorinated compds. in s.c.-CO2 is generally higher than their hydrocarbon analogs and fluorination of hydrocarbon compds. improves "CO2-philicity". Although dissoln. of a compd. in s.c.-CO2 (or any solvent) is a complex process, much can be learned by systematic examn. of solute-solvent interactions as a function of solute mol. properties in dimers and other small clusters. In the present study, Fourier-transform microwave spectroscopy and Symmetry Adapted Perturbation Theory (SAPT) calcns. have been used to examine intermol. interactions between CO2 and a series of fluorinated ethylene mols. with varying degree and position of fluorination (1-3 F atoms). While 1-fluoro-, 1,1-difluoro- and 1,1,2-trifluoroethylene...CO2 complexes are planar (with two isomers obsd. for 1-fluoroethylene), cis-1,2-difluoroethylene...CO2 is nonplanar. Although lowest energy structures predicted by MP2/6-311++G(2d,2p) calcns. are not always in agreement with obsd. configurations, SAPT calcns. provide binding energies consistent with the obsd. structures. We are now extending these studies to trimers contg. one fluorinated ethylene with two CO2 "solvent" mols. in order to gain further insight into structural and energetic changes as a solvation shell is formed. 

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3. Strong π-stacking causes unusually large anisotropic thermal expansion and thermochromism

   https://doi.org/10.1073/pnas.2106572118  

   Dharmarwardana, Madushani; Otten, Brooke M.; Ghimire, Mukunda M.; Arimilli, Bhargav S.; Williams, Christopher M.; Boateng, Stephen; Lu, Zhou; McCandless, Gregory T.; Gassensmith, Jeremiah J.; Omary, Mohammad A. (October 2021, Proceedings of the National Academy of Sciences)

   π-stacking in ground-state dimers/trimers/tetramers ofN-butoxyphenyl(naphthalene)diimide (BNDI) exceeds 50 kcal ⋅ mol⁻¹in strength, drastically surpassing that for the^*3[pyrene]₂excimer (∼30 kcal ⋅ mol⁻¹; formal bond order = 1) and similar to other weak-to-moderate classical covalent bonds. Cooperative π-stacking in triclinic (BNDI-T) and monoclinic (BNDI-M) polymorphs effects unusually large linear thermal expansion coefficients (α_a, α_b, α_c, β) of (452, −16.8, −154, 273) × 10⁻⁶⋅ K⁻¹and (70.1, −44.7, 163, 177) × 10⁻⁶⋅ K⁻¹, respectively. BNDI-T exhibits highly reversible thermochromism over a 300-K range, manifest by color changes from orange (ambient temperature) toward red (cryogenic temperatures) or yellow (375 K), with repeated thermal cycling sustained for over at least 2 y. 

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4. DFT study on binding of single and double methane with aromatic hydrocarbons and graphene: stabilizing CH…HC interactions between two methane molecules

   Jovian Lazare, Dalia Daggag (October 2020, Structural chemistry)

   null (Ed.)

   Density functional theory (DFT) calculations were used to examine the binding strength of one and two methane molecule(s) with graphene (62 and 186 carbon atoms) and model systems of aromatic hydrocarbons (benzene, pyrene, and coronene). We explored different possibilities of binding modes of methane such as one, two, and three C-H interacting with small π-systems. Two methane molecules were considered to bind from the same as well as opposite sides of the plane of benzene and other πsystems including graphene models. Our results show that methane molecule prefers to bind with three C-H…π interactions with all the π-systems except benzene. The preference of tripod configuration of methane on the surface of graphene systems strongly agrees with the neutron diffraction experiment of methane on graphitized carbon black. The binding strength is almost doubled by increasing the number of methane molecules from one to two. Importantly, two methane molecules prefer to bind on the same side rather than opposite sides of the plane of graphene due to stabilizing CH…HC interactions between them in addition to six CH…π interactions. Interestingly, binding strength contributions from CH…HC interactions (approx. 0.4–0.5 kcal/mol) of two methane molecules on the surface are analogous to methane dimer complex free from the surface of graphene. C-H stretching frequency shifts, bond lengths, and binding distances support the presence of CH…HC interactions between two methane molecules. Structures of complexes, binding energies, and C-H stretching frequency shifts agree with available experimental data 

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5. Non-covalent interactions involving π effect between organic cations in low-dimensional organic/inorganic hybrid perovskites

   https://doi.org/10.1063/5.0148876  

   Yan, Liang; Gloor, Camryn J.; Moran, Andrew M.; You, Wei (June 2023, Applied Physics Letters)

   Low-dimensional organic/inorganic hybrid perovskites (OIHPs) are a promising class of materials with a wide range of potential applications in optoelectronics and other fields since these materials can synergistically combine individual features of organic molecules and inorganics into unique properties. Non-covalent interactions are commonly observed in OIHPs, in particular, π-effect interactions between the organic cations. Such non-covalent interactions can significantly influence important properties of the low-dimensional OIHPs, including dielectric confinement, bandgap, photoluminescence, quantum efficiency, charge mobility, trap density, stability, and chirality. This perspective reviews recent studies of non-covalent interactions involving the π systems of organic cations in low-dimensional OIHPs. The analysis of crystal structures of low-dimensional OIHPs offers significant insight into understanding such non-covalent interactions and their impacts on specific properties of these OIHPs. The developed structure–property relationships can be used to engineer non-covalent interactions in low-dimensional OIHPs for applications. 

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