Sizing the role of London dispersion in the dissociation of all-meta tert-butyl hexaphenylethane

Rösel, Sören; Balestrieri, Ciro; Schreiner, Peter R.

doi:10.1039/c6sc02727j

Cited by 109 publications

(139 citation statements)

References 51 publications

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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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Section: Resultsmentioning

confidence: 93%

A Comprehensive Study on Tetraaryltetrabenzoporphyrins

Ruppel

Lungerich

Sturm

et al. 2020

Chemistry A European J

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“…[7] In addition severalo ther torsion balances following the same basic principle have been described. This has been utilized by Schneider, [10] Cockroft [11] or Schreiner [12] in order to evaluate interactionse ven as weak as dispersion forces in solution. However,i th as been pointed out that in solution the weak interactions are dominated/enforced by cohesive solvent effects.…”

Section: Introductionmentioning

confidence: 99%

Shedding Light on the Interactions of Hydrocarbon Ester Substituents upon Formation of Dimeric Titanium(IV) Triscatecholates in DMSO Solution

Kwamen

Schlottmann

Craen

et al. 2020

Chemistry A European J

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The dissociation of hierarchically formed dimeric triple lithium bridged triscatecholate titanium(IV)h elicates with hydrocarbyle sters as side groups is systematically investigated in DMSO. Primary alkyl, alkenyl, alkynyl as well as benzyl esters are studied in order to minimize steric effects close to the helicate core. The 1 HNMR dimerizationc onstants for the monomer-dimer equilibrium show some solvent dependent influenceo ft he side chains on the dimer stability.I nt he dimer,t he ability of the hydrocarbyle ster groups to aggregate minimizes their contacts with the solvent molecules. Due to this, most solvophobic alkyl groups show the highest dimerization tendency followed by alkenyls, alkynyls and finally benzyls.F urthermore, trends within the different groups of compounds can be observed. For example,t he dimer is destabilized by internal double or triple bonds due to p-p repulsion. As trong indication for solvent supported London dispersion interaction between the ester side groups is found by observation of an even/odd alternation of dimerizationconstants within the series of n-alkyls, n-W-alkenyls or n-W-alkynyls. This corresponds to the interaction of the parenth ydrocarbons, as documented by an even/odd melting point alternation. Figure 1. Wilcox molecular torsion balance. [a] A. Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.Figure 13. Dimerization constantsi n[ D 6 ]DMSOo fb enzyl derivatives Li[Li 3 (4 3 Ti) 2 ].Figure 14. Domains in whicht he dimerization constantso fa lkyl (green), alkenyl (red), alkynyl (blue) and benzyl ester (magenta) substituted complexes Li[Li 3 (L 3 Ti) 2 ]a re observed.

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“…Steric crowding effects as a means to stabilize other chemical systems have also been studied in Refs. [ ].…”

Section: Introductionmentioning

confidence: 99%

Intramolecular interactions in sterically crowded hydrocarbon molecules

Heßelmann

2017

J Comput Chem

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A molecular fragmentation method has been used to analyze the intramolecular interactions in the three molecules coupled diamantane, hexaphenylethane, and all-meta-tert-butyl substituted hexaphenylethane. The significance of these systems lies in the fact, that steric crowding effects enable a stabilization of the central carbon bond that possesses an extended length (1.6 to 1.7 Å) beyond conventional carbon-carbon bonds due to the steric repulsion of the attached hydrocarbon groups. The total stability of these molecules therefore depends on a delicate balance between attractive interaction forces on the one hand and on repulsive forces on the other hand. We have quantified the different interaction energy contributions using symmetry-adapted perturbation theory based on a density functional theory description of the monomers. It has been found that the attractive dispersion interactions increase more strongly with the level of crowding in the systems than the counteracting exchange interactions. This shows that steric crowding effects can have a significant impact on the structure and stability of large and branched molecules. © 2017 Wiley Periodicals, Inc.

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Sizing the role of London dispersion in the dissociation of all-meta tert-butyl hexaphenylethane

Abstract: The structure and dynamics of enigmatic hexa(3,5-di-tert-butylphenyl)ethane was characterized via NMR spectroscopy for the first time.

Cited by 109 publications

References 51 publications

A Comprehensive Study on Tetraaryltetrabenzoporphyrins

A Comprehensive Study on Tetraaryltetrabenzoporphyrins

Shedding Light on the Interactions of Hydrocarbon Ester Substituents upon Formation of Dimeric Titanium(IV) Triscatecholates in DMSO Solution

Intramolecular interactions in sterically crowded hydrocarbon molecules

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