London Dispersion Enables the Shortest Intermolecular Hydrocarbon H···H Contact

Rösel, Sören; Quanz, Henrik; Logemann, Christian; Becker, Jonathan; Mossou, Estelle; Cañadillas‐Delgado, Laura; Caldeweyher, Eike; Grimme, Stefan; Schreiner, Peter R.

doi:10.1021/jacs.7b01879

Cited by 147 publications

(137 citation statements)

References 61 publications

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“…This was not the case when the calculations were carried with M06‐2X, MP2, and SAPT0 since in these cases the BSSE corrected energies are always negative. Nevertheless, the above result is in agreement with recent reports by Schreiner and coworkers, who showed the London dispersion—the importance of which has been unappreciated over the years—can amount to several tens of kilocalories per mole when the cluster is reasonably large. Our conclusion on the polarizability of fluorine supports recent reports by Esterhuysen et al, and by others .…”

Section: Resultssupporting

confidence: 93%

Nature of halogen‐centered intermolecular interactions in crystal growth and design: Fluorine‐centered interactions in dimers in crystalline hexafluoropropylene as a prototype

Marques

Varadwaj

2019

J Comput Chem

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The wide occurrence of halogen‐centered noncovalent interactions in crystal growth and design prompted this study, which includes a mini review of recent advances in the field. Particular emphasis is placed on providing compelling theoretical evidence of the formation of these interactions between sites of positive electrostatic potential, as well as between sites of negative electrostatic potential, localized on the electrostatic surfaces of the bound fluorine atoms in a prototypical system, hexafluoropropylene (C3F6), upon its interaction with another same molecule to form (C3F6)2 dimers. The existence of σ‐ and π‐hole interactions is shown for the stable dimers. Even so, weakly bound interactions locally responsible in holding the molecular fragments together cannot and should not be overlooked since they are partly responsible for determining the overall geometry of the crystal. The results of combined quantum theory of atoms in molecules, molecular electrostatic surface potential, and reduced density gradient noncovalent interaction analyses showed that these latter interactions do indeed play a role in the stability and growth of crystalline C3F6 itself and the (C3F6)2 dimers. A symmetry adapted perturbation theory energy decomposition analysis leads to the conclusion that a great majority of the (C3F6)2 dimers examined are the consequence of dispersion (and electrostatics), with nonnegligible contribution from polarization, which together competes with an exchange repulsion component to determine the equilibrium geometries. In a few structures of the (C3F6)2 dimer, the fluorine is found to serve as a six‐center five‐bond donor/acceptor, as found for carbon in other systems (Malischewski and Seppelt, Angew. Chem. Int. Ed. 2017, 56, 368). © 2019 Wiley Periodicals, Inc.

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Section: Resultssupporting

confidence: 93%

Nature of halogen‐centered intermolecular interactions in crystal growth and design: Fluorine‐centered interactions in dimers in crystalline hexafluoropropylene as a prototype

Marques

Varadwaj

2019

J Comput Chem

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“…Soc . paper that has shown the importance of the r −6 dependence term in explaining the H•••H bonding between two electropositive hydrogen atoms in some complex systems . We expect that the stability of the stable

{normalB}_{24} {normalI}_{18}^{2 -}

complex reported in a recent article of the J. Phys.…”

Section: Resultsmentioning

confidence: 79%

Do surfaces of positive electrostatic potential on different halogen derivatives in molecules attract? like attracting like!

Varadwaj

Yamashita

2017

J Comput Chem

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Coulomb's law states that like charges repel, and unlike charges attract. However, it has recently been theoretically revealed that two similarly charged conducting spheres will almost always attract each other when both are in close proximity. Using multiscale first principles calculations, we illustrate practical examples of several intermolecular complexes that are formed by the consequences of attraction between positive atomic sites of similar or dissimilar electrostatic surface potential on interacting molecules. The results of the quantum theory of atoms in molecules and symmetry adapted perturbation theory support the attraction between the positive sites, characterizing the F•••X (X = F, Cl, Br) intermolecular interactions in a series of 20 binary complexes as closed-shell type, although the molecular electrostatic surface potential approach does not (a failure!). Dispersion that has an r dependence, where r is the equilibrium distance of separation, is found to be the sole driving force pushing the two positive sites to attract. © 2017 Wiley Periodicals, Inc.

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“…These CH–CH interactions lead to an in‐plane hexagonal surrounding of one molecule. While 4 forms nicely crystals, its solubility remains still very high in CH 2 Cl 2 , which is characteristic for London dispersion interactions . Even though the TBP‐skeletons show a similar distortion in all four structures, the examples show that meso ‐substituents have a distinct influence on the crystal‐packing, which allows for manifold manipulation.…”

Section: Resultsmentioning

confidence: 93%

A Comprehensive Study on Tetraaryltetrabenzoporphyrins

Ruppel

Lungerich

Sturm

et al. 2020

Chemistry A European J

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Tetraaryltetrabenzoporphyrins (TATBPs) show, due to their optoelectronic properties, rising potential as dyes in various fields of physical and biomedical sciences. However, unlike in the case of porphyrins, the potential structural diversity of TATBPs has been explored only to little extent, owed mainly to synthetic hurdles. Herein, we prepared a comprehensive library of 30 TATBPs and investigated their fundamental properties. We elucidated structural properties by X‐ray crystallography and found explanations for physical properties such as solubility. Fundamental electronic aspects were studied by optical spectroscopy as well as by electrochemistry and brought in context to the stability of the molecules. Finally, we were able to develop a universal synthetic protocol, utilizing a readily established isoindole synthon, which gives TATBPs in high yields, regardless of the nature of the used arylaldehyde and without meticulous chromatographic purifications steps. This work serves as point of orientation for scientists, that aim to utilize these molecules in materials, nanotechnological, and biomedical applications.

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London Dispersion Enables the Shortest Intermolecular Hydrocarbon H···H Contact

Cited by 147 publications

References 61 publications

Nature of halogen‐centered intermolecular interactions in crystal growth and design: Fluorine‐centered interactions in dimers in crystalline hexafluoropropylene as a prototype

Nature of halogen‐centered intermolecular interactions in crystal growth and design: Fluorine‐centered interactions in dimers in crystalline hexafluoropropylene as a prototype

Do surfaces of positive electrostatic potential on different halogen derivatives in molecules attract? like attracting like!

A Comprehensive Study on Tetraaryltetrabenzoporphyrins

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