Matrix effects on hydrogen bonding and proton transfer in fluoropyridine – HCl complexes

Soares, Camilla; Ley, Anna R.; Treacy, Patrick W.; Phillips, J. A.

doi:10.1039/d1cp04110j

Cited by 5 publications

(2 citation statements)

References 52 publications

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“…Moreover, the substitution position of the F‐functional group has a significant effect on the acidity of aromatic compounds, and the meta‐position substitution is more favorable for the basicity enhancement than the ortho‐position substitution, making m‐tfpe more easily to react with protons. [ 17 ] Besides, the calculated electron cloud density on pyridine groups of LUMO in HOF‐FJU‐40H is increased compared to HOF‐FJU‐40, which is ascribed to the protonated nitrogen atom that enhances the electron‐withstanding ability (Figure S28, Supporting Information). And, the calculated HOMO–LUMO energy gap decreases from HOF‐FJU‐40 to HOF‐FJU‐40H, which confirms that the protonation narrows the HOMO–LUMO energy gap, compatible with the redshifted change on emission fluorescence.…”

Section: Resultsmentioning

confidence: 99%

Smart‐Responsive HOF Heterostructures with Multiple Spatial‐Resolved Emission Modes toward Photonic Security Platform

Lv,

Liang,

Xiong

et al. 2023

Advanced Materials

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Luminescent hydrogen‐bonded organic frameworks (HOFs) with the unique dynamics and versatile functional sites hold great potential application in information security, yet most of responsive HOFs focus on the single‐component framework with restrained emission control, limiting further applications in advanced confidential information protection. Herein, we report the first smart‐responsive HOF heterostructure with multiple spatial‐resolved emission modes for covert photonic security platform. The HOF heterostructures are prepared by integrating different HOFs into a single microwire based on a hydrogen‐bond‐assisted epitaxial growth method. The distinct responsive behaviors of HOFs permit the heterostructure to simultaneously display the thermochromism via the framework transformation and the acidichromism via the protonation effect, thus generating multiple emission modes. The dual stimuli‐controlled spatial‐resolved emissive modes constitute the fingerprint of a heterostructure, and enable the establishment of the smart responsive photonic barcode with multiple convert states, which further demonstrate the dynamic coding capability and enhanced security in anti‐counterfeiting label application. These results offer a promising route to design function‐oriented smart responsive HOF micro‐devices towards advanced anticounterfeiting applications.This article is protected by copyright. All rights reserved

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Section: Resultsmentioning

confidence: 99%

Smart‐Responsive HOF Heterostructures with Multiple Spatial‐Resolved Emission Modes toward Photonic Security Platform

Lv,

Liang,

Xiong

et al. 2023

Advanced Materials

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“…Here, too, the study of isolated ions has been difficult. Instead, hydrogen bonding with simple Lewis acids has been used by many researchers as a proxy for protonation, since spectroscopic shifts of the hydrogen stretching motion of the acid have been correlated with the proton affinity of the base. − To this end, Lokshin and co-workers studied the hydrogen-bonded complexes of ferrocene and its alkyl derivatives with (CF 3 ) 3 COH in liquid xenon in the range of 165–270 K and concluded that the hydrogen bonding was to the cp ring of ferrocene. However, this conclusion was based solely on analogy to olefin complexes and was made without the benefit of computational chemistry (which was not available at the time).…”

Section: Introductionmentioning

confidence: 99%

Probing the Structure of the 1:1 Hydrogen-Bonded Complexes of Metallocenes with HCl

Ault

2024

J. Phys. Chem. A

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Matrix isolation infrared spectroscopy combined with density functional calculations has been used to form, isolate, and characterize the 1:1 hydrogen-bonded complexes of HCl with ferrocene and ruthenocene. Two unique structures were calculated for each complex, analogous to the two binding sites proposed for the attachment of proton to these metallocenes. The spectra, combined with calculated shifts of the H−Cl stretching mode, support the formation of a complex with the HCl hydrogen bonding to one of the cyclopentadienyl rings, exo to the plane of the ring. Evidence also was obtained for a second structure with the hydrogen of the HCl subunit directed toward the Fe or Ru center between the two cyclopentadienyl rings. This structure is similar to the proposed metal-bound proton structure based on earlier mass spectrometric and computational studies. Importantly, these results were supported by parallel experiments with DCl and the two metallocenes.

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Disentangling Acid‐Base Chemistry through Blue Shifting Hydrogen Bond Contributions

Kelly,

McNamara,

Gilbraith

et al. 2024

ChemPhysChem

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The blue shifting of vibrational frequencies in hydrogen bonded molecules, as observed in aqueous environments, has been attributed to local partial charge transfer from solvation. Here, we extrapolate the blue shift model to the stronger ionic interactions between hydrogen bond acceptors associated with protonation through augmented pH levels and competitive interactions with counter ion pairing. The chemical model we utilize in this work is the aqueous pyridine‐pyridinium equilibrium to characterize the blue shifts observed in the pyridinium chloride ionic system. The observed agreement between observed experimental and calculated spectral shifts shows that the blue shifting model can be extrapolated to stronger interactions and accurately describe the nature of the hydrogen bond.

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Matrix effects on hydrogen bonding and proton transfer in fluoropyridine – HCl complexes

Abstract: We report an extensive computational and spectroscopic study of several fluoropyridine–HCl complexes, and the parent, pyridine-HCl system. Matrix-IR spectra for pentafluoropyridine–HCl, 2,6-difluororpyridine–HCl, and 3,5-difluororpyridine–HCl in solid neon exhibit shifts for...

Cited by 5 publications

References 52 publications

Smart‐Responsive HOF Heterostructures with Multiple Spatial‐Resolved Emission Modes toward Photonic Security Platform

Smart‐Responsive HOF Heterostructures with Multiple Spatial‐Resolved Emission Modes toward Photonic Security Platform

Probing the Structure of the 1:1 Hydrogen-Bonded Complexes of Metallocenes with HCl

Disentangling Acid‐Base Chemistry through Blue Shifting Hydrogen Bond Contributions

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