Attenuation of London Dispersion in Dichloromethane Solutions

Pollice, Robert; Bot, Marek; Kobylianskii, Ilia J.; Shenderovich, Ilya G.; Chen, Peter

doi:10.1021/jacs.7b06997

Cited by 97 publications

(189 citation statements)

References 86 publications

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“…To address the reliability of the post-processing protocol for large complexes, Pollice et al 18 devised an example which is largely independent of the assumptions in this protocol. These authors synthesized a proton-bound dimer which can undergo two alternative dissociation reactions (hydrogen bond cleavage or O-NO bond cleavage) upon collision (see Figure 4).…”

Section: Possible Origins Of Discrepancies Between Calculated and Expmentioning

confidence: 99%

Calculation of Ligand Dissociation Energies in Large Transition-Metal Complexes

Husch

Freitag

Reiher

2018

J. Chem. Theory Comput.

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The accurate calculation of ligand dissociation (or equivalently, ligand binding) energies is crucial for computational coordination chemistry. Despite its importance, obtaining accurate ab initio reference data is difficult, and density-functional methods of uncertain reliability are chosen for feasibility reasons. Here, we consider advanced coupled-cluster and multiconfigurational approaches to reinvestigate our WCCR10 set of 10 gas-phase ligand dissociation energies [ J. Chem. Theory Comput. 2014, 10, 3092]. We assess the potential multiconfigurational character of all molecules involved in these reactions with a multireference diagnostic [ Mol. Phys. 2017, 115, 2110] in order to determine where single-reference coupled-cluster approaches can be applied. For some reactions of the WCCR10 set, large deviations of density-functional results including semiclassical dispersion corrections from experimental reference data had been observed. This puzzling observation deserves special attention here, and we tackle the issue (i) by comparing to ab initio data that comprise dispersion effects on a rigorous first-principles footing and (ii) by a comparison of density-functional approaches that model dispersion interactions in various ways. For two reactions, species exhibiting nonnegligible static electron correlation were identified. These two reactions represent hard problems for electronic structure methods and also for multireference perturbation theories. However, most of the ligand dissociation reactions in WCCR10 do not exhibit static electron correlation effects, and hence, we may choose standard single-reference coupled-cluster approaches to compare with density-functional methods. For WCCR10, the Minnesota M06-L functional yielded the smallest mean absolute deviation of 13.2 kJ mol out of all density functionals considered (PBE, BP86, BLYP, TPSS, M06-L, PBE0, B3LYP, TPSSh, and M06-2X) without additional dispersion corrections in comparison to the coupled-cluster results, and the PBE0-D3 functional produced the overall smallest mean absolute deviation of 4.3 kJ mol. The agreement of density-functional results with coupled-cluster data increases significantly upon inclusion of any type of dispersion correction. It is important to emphasize that different density-functional schemes available for this purpose perform equally well. The coupled-cluster dissociation energies, however, deviate from experimental results on average by 30.3 kJ mol. Possible reasons for these deviations are discussed.

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Section: Possible Origins Of Discrepancies Between Calculated and Expmentioning

confidence: 99%

Calculation of Ligand Dissociation Energies in Large Transition-Metal Complexes

Husch

Freitag

Reiher

2018

J. Chem. Theory Comput.

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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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“…Importantly,t he clusterformation ability is not related to the solubility of the molecules in for example, CH 2 Cl 2 or CHCl 3 , which does not only allow the clear analysis by NMR spectroscopy in solution (compareF igures S12-S15 in the Supporting Information), but correlates well to the latest observations by Pollice et al,w ho found the attenuation of LD in CH 2 Cl 2 solutions. [11] Aq ualitative depiction can be summarized as the following:c luster size: 4 ! 3 > 2 > 1 !…”

Section: Resultsmentioning

confidence: 99%

“…Bulky substituents like cyclohexyl, adamantly,o rtert-butyl (tBu) groups,a re often installed under the premise of Pauli repulsion, thus as sterically demanding and potentially solubilizing groups. [2,3] However,r ecent theoretical [4][5][6][7] and experimental work [8][9][10][11] led to the rise of so-called dispersion-energy-donors (DEDs). The attractive interactions based on oscillating dipole moments, called Londond ispersion (LD), [12,13] are the foundation of s-s interactions in DEDs, as they are true for tert-butyl groups.Still, on paper, tBu groups appear as bulky substituents and indeed, usually solubilizing effects are mostly observed.…”

Section: Introductionmentioning

confidence: 99%

Superbenzene–Porphyrin Gas‐Phase Architectures Derived from Intermolecular Dispersion Interactions

Lungerich

Hitzenberger

Hampel

et al. 2018

Chemistry A European J

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A systematic series of superbenzene-porphyrin conjugates was synthesized and characterized. All conjugates show a high degree of cluster formation that correlates to the amount of tert-butylated hexa-peri-hexabenzocoronenes (tBuHBCs) attached to the porphyrin's periphery. Determined by mass spectrometry and X-ray diffraction, van der Waals (vdW) interactions like London dispersions (LD), stemming from solubilizing tert-butyl groups, were identified to be the major reason for the cluster formation. Cluster sizes comprised of more than twenty molecules with masses up to 70 000 Da were observed, which are rare examples of large architectures based on synthetic functional molecules, assembled by dispersion interactions. Novel strategies towards the design of solution processable functional materials, capable of dynamic transformations based on non-covalent synthesis can be envisioned.

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Attenuation of London Dispersion in Dichloromethane Solutions

Cited by 97 publications

References 86 publications

Calculation of Ligand Dissociation Energies in Large Transition-Metal Complexes

Calculation of Ligand Dissociation Energies in Large Transition-Metal Complexes

A Comprehensive Study on Tetraaryltetrabenzoporphyrins

Superbenzene–Porphyrin Gas‐Phase Architectures Derived from Intermolecular Dispersion Interactions

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