Mesoionic compounds: the role of intermolecular interactions in their crystalline design

Martins, Marcos A. P.; Lima, Péricles Souza; Weimer, Gustavo H.; Oliveira, Leonardo P.; Souza, Helivaldo Diógenes da Silva; Fiss, Gabriela F.; Bonacorso, Hélio G.

doi:10.1039/d3ce00554b

Cited by 3 publications

(3 citation statements)

References 59 publications

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“…We have already demonstrated experimentally, through CD-NMR techniques, that more energetically stable blocks (or dimers) are presented in saturated solutions. These blocks correlate with the intermolecular interactions present in the demarcation of the supramolecular cluster. ,, …”

Section: Resultsmentioning

confidence: 90%

“…These blocks correlate with the inter-molecular interactions present in the demarcation of the supramolecular cluster. 32,57,58 Analyzing the graphs, we noticed three distinct profiles for compounds 9, 16, and 10. Starting the exemplary discussion with compound 9, two dimers stand out energetically and topologically, namely, dimers M1•••M7 and M1•••M14, indicating that this may be the initial block that will form and persevere in solution.…”

Section: ■ Results and Discussionmentioning

confidence: 94%

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[2]Rotaxane Solvates: Insights into the Presence of Solvents in the Crystal Lattice

Farias,

Weimer,

Kunz

et al. 2024

Crystal Growth & Design

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During synthesis and purification, compounds are exposed to various solvents. These solvents can, at times, assemble in the solid state. This association can arise from intermolecular interactions, allowing solvent molecules to bind with chemical substances and resulting in a unique crystalline structure known as a solvate. Nevertheless, such an association with solvents can substantially alter the properties of the compounds. In the crystalline solid state, the occurrence of solvates is recurrent among mechanically interlocked molecules (MIMs), including rotaxanes; however, solvates are frequently considered incidental or inconsequential. In this context, we sought to investigate the role and relevance of solvent molecules in the crystallization process of rotaxanes by systematically analyzing 24 models, employing the supramolecular cluster as a demarcation tool and using tetralactam-macrocycle based [2]rotaxanes. In general, the most frequently occurring [2]rotaxane solvates are with chloroform and water molecules (∼66%). The occurrence of solvates does not follow any rule or pattern, implying that similar structures can and do contain different solvates in varying proportions. By the crystallization mechanisms proposed, it was feasible to determine at which stage of the crystallization process the solvates are formed, and the energetic and topological contributions of the solvent molecules during crystallization were assessed. The most rotaxanes "trap" solvent molecules during crystallization, and interestingly, in certain instances, these solvent molecules are essential for crystallization, contributing up to 40% of the total stabilization energy of the supramolecular cluster.

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Section: Resultsmentioning

confidence: 90%

Section: ■ Results and Discussionmentioning

confidence: 94%

[2]Rotaxane Solvates: Insights into the Presence of Solvents in the Crystal Lattice

Farias,

Weimer,

Kunz

et al. 2024

Crystal Growth & Design

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“…1 Data on contact area and stabilization energy obtained by supramolecular cluster demarcation has been extensively employed for crystalline systems of uncharged organic molecules obtained as monocomponents, cocrystals, solvates, and polymorphs. 2,10–21 This approach has also been applied to charged molecules, including dicationic ionic liquids, 22 semicarbazone metal complexes, 23 ammonium halide salts, 3 and mesoionic compounds, 24 to shed more light on the significance of each intermolecular interaction in the crystalline lattice formation.…”

Section: Introductionmentioning

confidence: 99%

Ammonium carboxylate salts: the additivity of intermolecular interaction energies in charged organic compounds

Rosa,

Lima,

Bonacorso

et al. 2024

CrystEngComm

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A New Model for Proposing Crystallization Mechanisms at the Molecular Level Based on Energetic and Topological Data of Supramolecular Interactions: An Application to Halogenated Anilines

Teixeira Campos,

Canez Lemos Souza,

André Pires

2024

Crystal Growth & Design

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In this work, a new model for proposing crystallization mechanisms at the molecular level was created, based mainly on theoretical energetic and topological data of intermolecular and supramolecular interactions. Initially, a supramolecular study was conducted on anilines substituted with halogens in the ortho or para positions. All of the compounds had a molecular coordination number equal to 14. In these structures, all the intermolecular interactions were checked and classified, and their robustness was evaluated in terms of energy using density functional theory and their contribution at each contact point using QTAIM theory. The substantial number of interactions considered weaker such as C–H···X, C–H···C, and N–H···C contribute more to stabilizing the cluster than the N–H···N interactions, considered stronger, which have a much smaller number of occurrences. In order to validate the energy data of the intermolecular interactions, lattice energy data (theoretical) and sublimation enthalpy data (experimental) were compared, which revealed an excellent correlation and a notable trend for most of the compounds. Finally, crystallization mechanisms were proposed, starting from the strongest interaction present in the first coordination sphere. Starting from the supramolecular chain (1D) formed, hypotheses were created to approximate these structures in order to determine which one brings greater stability to the system and suggest the formation of supramolecular layers (2D), until a structure with growth in three directions is achieved. All of the compounds required at least four stages to achieve a 3D structure.

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Mesoionic compounds: the role of intermolecular interactions in their crystalline design

Abstract: The quest for understanding crystal structures using supramolecular cluster demarcation has been applied to various uncharged compounds, and, more recently, it has also been applied to charged compounds in...

Cited by 3 publications

References 59 publications

[2]Rotaxane Solvates: Insights into the Presence of Solvents in the Crystal Lattice

[2]Rotaxane Solvates: Insights into the Presence of Solvents in the Crystal Lattice

Ammonium carboxylate salts: the additivity of intermolecular interaction energies in charged organic compounds

A New Model for Proposing Crystallization Mechanisms at the Molecular Level Based on Energetic and Topological Data of Supramolecular Interactions: An Application to Halogenated Anilines

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