Competing Supramolecular Forces: Boron Coordination vs π-π Stacking

This study explores the impact of fluorination levels in azopyridine Lewis bases on their ability to direct the formation of B←N coordination adducts or cocrystals with phenylboronic ester. We hypothesize that the degree of fluorination can be used as a tool to control the outcome of supramolecular bonding competition, thus influencing complex self-assembly. A series of azopyridines with varying degrees of fluorination were synthesized and reacted with phenylboronic ester. Their structures were analyzed using Hartree-Fock calculations, Hirshfeld surface analyses, and single crystal X-ray diffraction to assess the impact of fluorination on supramolecular interactions. The study reveals that azopyridines with up to two fluorine atoms form B←N coordination complexes, while perfluorinated azopyridine leads to cocrystal formation through π-stacking interactions. The outcome depends on the electronic properties of the pyridyl nitrogens, influenced by the level of fluorination. Fluorination in azopyridine Lewis bases serves as an effective strategy to modulate supramolecular bonding competition between boron coordination and π-stacking. This approach enables the selective formation of desired supramolecular structures, highlighting the utility of fluorination in guiding the self-assembly process. The findings have implications for the development of functional materials and 2D devices, offering a novel method for controlling the architecture of supramolecular assemblies

Confinement and Separation of Benzene from an Azeotropic Mixture Using a Chlorinated B←N Adduct

Separations of azeotropic mixtures are typically carried out using energy-demanding processes (e.g., distillation). Here, we report the capacity of a self-assembled chlorinated boronic ester-based adduct to confine acetonitrile and benzene in channels upon crystallization. The solvent confinement occurs via a combination of hydrogen bonding and [π···π] interactions. Quantitative separation of benzene from an azeotropic 1:1 mixture of a benzene/acetonitrile (v/v), and methanol is achieved through crystallization with the chlorinated adduct by complementary [C–H···O] and [C–H···π] interactions. Inclusion behavior is rationalized by molecular modeling and crystallographic analysis. The chlorinated boronic ester adduct shows the potential of modularity via isosteric substitution for the separation of challenging chemical mixtures (e.g., azeotropes)

Engineering Lipophilic Aggregation of Adapalene and Adamantane-Based Cocrystals via van der Waals Forces and Hydrogen Bonding

Lipophilic aggregation using adamantanes is a widely exploited molecular property in medicinal and materials chemistry. Adamantanes are traditionally installed to molecular units via covalent bonds. However, the noncovalent installation of adamantanes has been relatively underexplored and presents the potential to bring properties associated with adamantanes to molecules without affecting their intrinsic properties (e.g., pharmacophores). Here, we systematically study a series of adamantanecarboxylic acids with varying substitution levels of methyl groups and their cocrystals with bipyridines. Specifically, single-crystal X-ray diffraction shows that while the directionality of single-component adamantanes is notably sensitive to changes in methyl substitution, hydrogen-bonded cocrystals with bipyridines show consistent and robust packing due to π-stacking predominance. Our observations are supported by Hirshfeld surface and energy framework analyses. The applicability of cocrystal formation of adamantanes bearing carboxylic acids was used to generate the first cocrystals of adapalene, an adamantane-bearing retinoid used for treating acne vulgaris. We envisage our study to inspire noncovalent (i.e., cocrystal) installation of adamantanes to generate lipophilic aggregation in multicomponent systems

Measurement of exclusive J/ψJ/\psi and ψ(2S)\psi(2S) production at s=13\sqrt{s}=13 TeV

International audienceMeasurements are presented of the cross-section for the central exclusive production of $J/\psi\to\mu^+\mu^-$ and $\psi(2S)\to\mu^+\mu^-$ processes in proton-proton collisions at $\sqrt{s} = 13$ TeV with 2016-2018 data. They are performed by requiring both muons to be in the LHCb acceptance (with pseudorapidity $2<\eta_{\mu^\pm} < 4.5$) and mesons in the rapidity range $2.0 < y < 4.5$. The integrated cross-section results are \begin{equation*} \sigma_{J/\psi\to\mu^+\mu^-}(2.0<y_{J/\psi}<4.5,2.0<\eta_{\mu^\pm} < 4.5) = 400 \pm 2 \pm 5 \pm 12 \,{\rm pb}\,, \end{equation*}\begin{equation*} \sigma_{\psi(2S)\to\mu^+\mu^-}(2.0<y_{\psi(2S)}<4.5,2.0<\eta_{\mu^\pm} < 4.5) = 9.40 \pm 0.15 \pm 0.13 \pm 0.27 \,{\rm pb}\,, \end{equation*} where the uncertainties are statistical, systematic and due to the luminosity determination. In addition, a measurement of the ratio of $\psi(2S)$ and $J/\psi$ cross-sections, at an average photon-proton centre-of-mass energy of 1 TeV, is performed, giving \begin{equation*} \frac{\sigma_{\psi(2S)}}{\sigma_{J/\psi}} = 0.1763 \pm 0.0029 \pm 0.0008 \pm 0.0039 \,, \end{equation*} where the first uncertainty is statistical, the second systematic and the third due to the knowledge of the involved branching fractions. For the first time, the dependence of the $J/\psi$ and $\psi(2S)$ cross-sections on the total transverse momentum transfer is determined in $pp$ collisions and is found consistent with the behaviour observed in electron-proton collisions

Measurement of exclusive J/ψJ/\psi and ψ(2S)\psi(2S) production at s=13\sqrt{s}=13 TeV

International audienceMeasurements are presented of the cross-section for the central exclusive production of $J/\psi\to\mu^+\mu^-$ and $\psi(2S)\to\mu^+\mu^-$ processes in proton-proton collisions at $\sqrt{s} = 13$ TeV with 2016-2018 data. They are performed by requiring both muons to be in the LHCb acceptance (with pseudorapidity $2<\eta_{\mu^\pm} < 4.5$) and mesons in the rapidity range $2.0 < y < 4.5$. The integrated cross-section results are \begin{equation*} \sigma_{J/\psi\to\mu^+\mu^-}(2.0<y_{J/\psi}<4.5,2.0<\eta_{\mu^\pm} < 4.5) = 400 \pm 2 \pm 5 \pm 12 \,{\rm pb}\,, \end{equation*}\begin{equation*} \sigma_{\psi(2S)\to\mu^+\mu^-}(2.0<y_{\psi(2S)}<4.5,2.0<\eta_{\mu^\pm} < 4.5) = 9.40 \pm 0.15 \pm 0.13 \pm 0.27 \,{\rm pb}\,, \end{equation*} where the uncertainties are statistical, systematic and due to the luminosity determination. In addition, a measurement of the ratio of $\psi(2S)$ and $J/\psi$ cross-sections, at an average photon-proton centre-of-mass energy of 1 TeV, is performed, giving \begin{equation*} \frac{\sigma_{\psi(2S)}}{\sigma_{J/\psi}} = 0.1763 \pm 0.0029 \pm 0.0008 \pm 0.0039 \,, \end{equation*} where the first uncertainty is statistical, the second systematic and the third due to the knowledge of the involved branching fractions. For the first time, the dependence of the $J/\psi$ and $\psi(2S)$ cross-sections on the total transverse momentum transfer is determined in $pp$ collisions and is found consistent with the behaviour observed in electron-proton collisions

Measurement of exclusive J/ψJ/\psi and ψ(2S)\psi(2S) production at s=13\sqrt{s}=13 TeV

International audienceMeasurements are presented of the cross-section for the central exclusive production of $J/\psi\to\mu^+\mu^-$ and $\psi(2S)\to\mu^+\mu^-$ processes in proton-proton collisions at $\sqrt{s} = 13$ TeV with 2016-2018 data. They are performed by requiring both muons to be in the LHCb acceptance (with pseudorapidity $2<\eta_{\mu^\pm} < 4.5$) and mesons in the rapidity range $2.0 < y < 4.5$. The integrated cross-section results are \begin{equation*} \sigma_{J/\psi\to\mu^+\mu^-}(2.0<y_{J/\psi}<4.5,2.0<\eta_{\mu^\pm} < 4.5) = 400 \pm 2 \pm 5 \pm 12 \,{\rm pb}\,, \end{equation*}\begin{equation*} \sigma_{\psi(2S)\to\mu^+\mu^-}(2.0<y_{\psi(2S)}<4.5,2.0<\eta_{\mu^\pm} < 4.5) = 9.40 \pm 0.15 \pm 0.13 \pm 0.27 \,{\rm pb}\,, \end{equation*} where the uncertainties are statistical, systematic and due to the luminosity determination. In addition, a measurement of the ratio of $\psi(2S)$ and $J/\psi$ cross-sections, at an average photon-proton centre-of-mass energy of 1 TeV, is performed, giving \begin{equation*} \frac{\sigma_{\psi(2S)}}{\sigma_{J/\psi}} = 0.1763 \pm 0.0029 \pm 0.0008 \pm 0.0039 \,, \end{equation*} where the first uncertainty is statistical, the second systematic and the third due to the knowledge of the involved branching fractions. For the first time, the dependence of the $J/\psi$ and $\psi(2S)$ cross-sections on the total transverse momentum transfer is determined in $pp$ collisions and is found consistent with the behaviour observed in electron-proton collisions

Measurement of exclusive J/ψJ/\psi and ψ(2S)\psi(2S) production at s=13\sqrt{s}=13 TeV

International audienceMeasurements are presented of the cross-section for the central exclusive production of $J/\psi\to\mu^+\mu^-$ and $\psi(2S)\to\mu^+\mu^-$ processes in proton-proton collisions at $\sqrt{s} = 13$ TeV with 2016-2018 data. They are performed by requiring both muons to be in the LHCb acceptance (with pseudorapidity $2<\eta_{\mu^\pm} < 4.5$) and mesons in the rapidity range $2.0 < y < 4.5$. The integrated cross-section results are \begin{equation*} \sigma_{J/\psi\to\mu^+\mu^-}(2.0<y_{J/\psi}<4.5,2.0<\eta_{\mu^\pm} < 4.5) = 400 \pm 2 \pm 5 \pm 12 \,{\rm pb}\,, \end{equation*}\begin{equation*} \sigma_{\psi(2S)\to\mu^+\mu^-}(2.0<y_{\psi(2S)}<4.5,2.0<\eta_{\mu^\pm} < 4.5) = 9.40 \pm 0.15 \pm 0.13 \pm 0.27 \,{\rm pb}\,, \end{equation*} where the uncertainties are statistical, systematic and due to the luminosity determination. In addition, a measurement of the ratio of $\psi(2S)$ and $J/\psi$ cross-sections, at an average photon-proton centre-of-mass energy of 1 TeV, is performed, giving \begin{equation*} \frac{\sigma_{\psi(2S)}}{\sigma_{J/\psi}} = 0.1763 \pm 0.0029 \pm 0.0008 \pm 0.0039 \,, \end{equation*} where the first uncertainty is statistical, the second systematic and the third due to the knowledge of the involved branching fractions. For the first time, the dependence of the $J/\psi$ and $\psi(2S)$ cross-sections on the total transverse momentum transfer is determined in $pp$ collisions and is found consistent with the behaviour observed in electron-proton collisions

Measurement of exclusive J/ψJ/\psi and ψ(2S)\psi(2S) production at s=13\sqrt{s}=13 TeV

International audienceMeasurements are presented of the cross-section for the central exclusive production of $J/\psi\to\mu^+\mu^-$ and $\psi(2S)\to\mu^+\mu^-$ processes in proton-proton collisions at $\sqrt{s} = 13$ TeV with 2016-2018 data. They are performed by requiring both muons to be in the LHCb acceptance (with pseudorapidity $2<\eta_{\mu^\pm} < 4.5$) and mesons in the rapidity range $2.0 < y < 4.5$. The integrated cross-section results are \begin{equation*} \sigma_{J/\psi\to\mu^+\mu^-}(2.0<y_{J/\psi}<4.5,2.0<\eta_{\mu^\pm} < 4.5) = 400 \pm 2 \pm 5 \pm 12 \,{\rm pb}\,, \end{equation*}\begin{equation*} \sigma_{\psi(2S)\to\mu^+\mu^-}(2.0<y_{\psi(2S)}<4.5,2.0<\eta_{\mu^\pm} < 4.5) = 9.40 \pm 0.15 \pm 0.13 \pm 0.27 \,{\rm pb}\,, \end{equation*} where the uncertainties are statistical, systematic and due to the luminosity determination. In addition, a measurement of the ratio of $\psi(2S)$ and $J/\psi$ cross-sections, at an average photon-proton centre-of-mass energy of 1 TeV, is performed, giving \begin{equation*} \frac{\sigma_{\psi(2S)}}{\sigma_{J/\psi}} = 0.1763 \pm 0.0029 \pm 0.0008 \pm 0.0039 \,, \end{equation*} where the first uncertainty is statistical, the second systematic and the third due to the knowledge of the involved branching fractions. For the first time, the dependence of the $J/\psi$ and $\psi(2S)$ cross-sections on the total transverse momentum transfer is determined in $pp$ collisions and is found consistent with the behaviour observed in electron-proton collisions