Tuning charge-assisted and weak hydrogen bonds in molecular complexes of the proton sponge DMAN by acid co-former substitution

Saunders, Lucy K.; Nowell, Harriott; Spencer, Helen C. E.; Hatcher, Lauren E.; Shepherd, Helena J.; Thomas, Lynne H.; Jones, Charlotte L.; Teat, Simon J.; Raithby, Paul R.; Wilson, Chick C.

doi:10.1039/c8ce00443a

Cited by 6 publications

(2 citation statements)

References 37 publications

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“…This region is often referred to as the salt cocrystal continuum. ,,, It comprises not only examples of structures with proton transfer or hydrogen bonding, but also many cases that elude such classification, especially when donor–acceptor bond distances are short . As a result, structures with proton transfer and short donor–acceptor distances have variously been referred to as salts, ,, charge-assisted short-strong hydrogen bonds (SSHBs), , or proton transferred interactions. ,,,, Cocrystals are usually described as hydrogen-bonded or containing neutral hydrogen bonds, ,,, but short donor–acceptor distances can, for example, result in SSHBs in which the proton is partially transferred, shared between the donor and acceptor, blurring the boundary between salts and cocrystals. Moreover, systems with multiple options for donor–acceptor pairing often exhibit two or more types of interactions within one crystal structurethe systems to be examined in this paper include an example of such cases …”

Section: Introductionmentioning

confidence: 99%

Proton Transfer on the Edge of the Salt/Cocrystal Continuum: X-Ray Photoelectron Spectroscopy of Three Isonicotinamide Salts

Edwards

Saunders

Pallipurath

et al. 2021

Crystal Growth & Design

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X-ray photoelectron spectroscopy (XPS) has emerged as a technique that allows for characterization and classification of hydrogen bonding and proton transfer interactions in organic crystal structures, in a way that is complementary to crystallography by X-ray or neutron diffraction. Here, we analyze the nitrogen 1s core-level binding energies (BEs) of isonicotinamide (IN) systems with proton transfer between donor and acceptor groups at short distances. We show how a careful calibration of the BE scale places these salt systems correctly on the edge of the so-called salt–cocrystal continuum. We show how performing a fitting analysis of the data that is consistent with elemental analysis, expected stoichiometry, and quantification of adventitious carbon contamination facilitates the determination of absolute BEs with accuracy and reproducibility within ±0.1 eV. The determined N 1s core-level BEs of the protonated IN acceptors suggest that the local geometric arrangements of the donor, acceptor, and proton can influence the N 1s core-level BE significantly.

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Section: Introductionmentioning

confidence: 99%

Proton Transfer on the Edge of the Salt/Cocrystal Continuum: X-Ray Photoelectron Spectroscopy of Three Isonicotinamide Salts

Edwards

Saunders

Pallipurath

et al. 2021

Crystal Growth & Design

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“…These bonds are particularly useful in driving the synthesis of synthons when the crystallizing species are conjugate acid-base, which means they differ chemically only by a proton. [25][26][27] In recent years, halogen bonding has evolved from a scientific curiosity into one of the most appealing noncovalent interactions for constructing supramolecular assemblies. This evolution has led to organic materials with halogen bonding becoming highly valuable for various applications in material sciences, biomolecular recognition, and drug design.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Growth, Structural Characterization, Supramolecular Chemistry, and Theoretical Calculations of Methylenium Salts of Benzenesulfonates

Ullah,

Li,

Huang

et al. 2024

ChemistrySelect

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The current investigation describes the synthesis of four novel methylene blue (MB) salts of benzene sulfonate derivatives, featuring bulky anionic groups. The process involves treating chloride salt of MB with sodium salts of 4‐aminobenzene sulfonate, 4‐styrenebenzene sulfonate, 3,7‐naphthalene disulfonate, and anthraquinone‐1,5‐naphthalene disulfonate to substitute the chloride ion with benzoate sulfonate anion in MB‐chloride. The synthesis includes quaternizing MB‐chloride with the corresponding benzene sulfonate in minimal aqueous solvent to promote precipitation. The resultant precipitates were subsequently dissolved in an appropriate solvent to enable the crystallization of the ultimate product. The dissolution occurs either at ambient temperature or with heat. The crystals of the resultant salts were characterized using various analytical techniques like UV‐visible, and FT‐IR spectroscopy, TGA, single crystal X‐ray diffraction and powder X‐ray diffraction analysis. The UV‐visible spectroscopic results, frontier molecular orbital, density of states, molecular electrostatic potentials, and HOMO‐LUMO energy gaps were estimated by DFT. Structural analysis revealed that supramolecular structure of compounds achieved stabilization through electrostatic interactions, a diverse range of both conventional and non‐conventional hydrogen bonds, π–π stacking interactions, and other short‐range interactions. The investigation delves into intricate details and offers a thorough discussion of the fundamental principles that contribute to the formation and stabilization of supramolecular structures.

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Organic salt versus salt cocrystal: thermal behavior, structural and photoluminescence investigations

Crişan¹,

Petric²,

Vlase

et al. 2021

J Therm Anal Calorim

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Tuning charge-assisted and weak hydrogen bonds in molecular complexes of the proton sponge DMAN by acid co-former substitution

Abstract: Varying the electronic character of the acid co-former substituent group predictably alters weak and strong intermolecular interactions.

Cited by 6 publications

References 37 publications

Proton Transfer on the Edge of the Salt/Cocrystal Continuum: X-Ray Photoelectron Spectroscopy of Three Isonicotinamide Salts

Proton Transfer on the Edge of the Salt/Cocrystal Continuum: X-Ray Photoelectron Spectroscopy of Three Isonicotinamide Salts

Synthesis, Crystal Growth, Structural Characterization, Supramolecular Chemistry, and Theoretical Calculations of Methylenium Salts of Benzenesulfonates

Organic salt versus salt cocrystal: thermal behavior, structural and photoluminescence investigations

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