Competition between the donor and acceptor hydrogen bonds of the threads in the formation of [2]rotaxanes by clipping reaction

Martins, Marcos A. P.; Zimmer, Geórgia C.; Rodrigues, Leticia V.; Orlando, Tainára; Buriol, Lilian; Alajarı́n, Mateo; Berná, José; Frizzo, Clarissa P.; Bonacorso, Hélio G.; Zanatta, Nilo

doi:10.1039/c7nj02443f

Cited by 13 publications

(28 citation statements)

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“…The interaction stabilization energies of each “furcated” system were obtained using the G AI analysis, following a procedure already reported in studies using different kind of molecules , , , , . The G AI analysis furnished the energy of each atom ··· atom interaction correlating Quantum Theory of Atoms in Molecules (QTAIM) data and intercomponent stabilization energy.…”

Section: Resultsmentioning

confidence: 99%

[2]Rotaxanes Bearing a Tetralactam Macrocycle: The Role of a Trifurcated Hydrogen Bond in the Crystalline State

et al. 2019

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This study investigated the proper classification and quantification of intercomponent trifurcated hydrogen bonds, in the crystalline state, of rotaxanes bearing a tetralactam Leigh‐type macrocycle. Quantum mechanical calculations were carried out to obtain the interaction paths and their stabilization energies. In general, the use and necessity of fragmentation in types of interaction have been reported in the literature, although they are commonly performed only using a geometric approach. This results in N–H···O interactions that are indicated as the main interactions between components, neglecting other possible interactions. The use of energetic fragmentation was demonstrated here under an appropriate demarcation considering all interactions and showing the existence and role of the C–H···O interaction. The C–H···O interactions showed similar energy to N–H···O interactions with average values around –4.75 kcal mol–1 and –4.60 kcal mol–1, respectively. This revealed that the three hydrogen bonds are part of a cooperative set of interactions with a similar contribution. The trifurcated hydrogen bonds presented high contribution in the total intercomponent stabilization energy of the rotaxanes, with an average value of 51 % in the studied series.

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Section: Resultsmentioning

confidence: 99%

[2]Rotaxanes Bearing a Tetralactam Macrocycle: The Role of a Trifurcated Hydrogen Bond in the Crystalline State

et al. 2019

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“…Our research group has already reported the synthetic procedures to obtain these compounds. 46 Also, the packing characteristics of some structures involved in obtaining [2]rotaxanes with regard to NH•••OC interactions and the participation of tert-butyl groups in selfassembly and heteroassembly have also been previously discussed. 46 Initially, a molecular approach was carried out for the structural study development considering the flexible series of compounds 1a−d and 2a−d (Scheme 1).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…The molecules present in this study were initially synthesized as threads in [2]rotaxane formation. 46 Rotaxanes are molecules composed of macrocycles trapped on a thread with two bulky groups. These threads are equipped with a 1,4diamide linker and 1,3-or 1,5-tert-butylpyrazole regioisomers and present donor (N−H) and acceptor (CO) hydrogen bond groups (Scheme 1).…”

Section: ■ Introductionmentioning

confidence: 99%

“…Additionally, the study showed that the 1,3-tert-butylpyrazole thread has only hydrogen bond acceptor characteristics, unlike the 1,5-tert-butylpyrazole thread, which showed good hydrogen bond acceptor and donor properties. 46 Moreover, during the study of threads, the different polymorphs obtained proved to be potential models for investigating polymorphism in this class of molecules.…”

Section: ■ Introductionmentioning

confidence: 99%

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Packing and Conformational Polymorphism in 1,2-Bis(aminocarbonyl(1-tert-butyl-1H-pyrazol-(3)5-yl))ethanes: Illuminating Examples of Highly Flexible Molecules

Zimmer

Pagliari

Solner

et al. 2021

Crystal Growth & Design

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Insights into the occurrence of packing and conformational polymorphs and anhydrous/hydrate forms of 1,2-bis(aminocarbonyl(1-tert-butyl-1H-pyrazol-[3]5-yl))ethanes with the substituents R = Me (a), F-4-Ph (b), Cl-4-Ph (c), and Br-4-Ph (d) in positions 5 (1) and 3 (2) of the pyrazole rings are presented. In this series, two molecular forms were observed, linear and folded. Compound 1a revealed an illuminating and rare example of a highly flexible molecule with packing polymorphism. The molecular stacking and absence of NH···OC interactions promoted polymorph growth. Structure 2a showed chains driven by NH···OC bonds in the anhydrous form and closed dimers by water binding the molecules (NHamide···OHwt···COamide) in the hydrate form. Two different forms were observed for conformational polymorph 2d (linear and folded). The folded form was about −10 kcal mol–1 more stable than the linear form, showing significant crystalline packing differences. This occurrence is attributed to the rotation of the amide groups through the NH···OC bonds. The linear shape showed a higher stabilization energy for NH···OC bonds and a cluster −6 kcal mol–1 more stable than polymorph 2dI. Compounds 1b–d and 2b-c also had their crystal growth proposed and features highlighted.

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“…When designing new molecules with enhanced properties, analysis should go beyond merely investigating the molecular structure [ 1 , 2 ]. It is necessary to understand the supramolecular environment, especially in the self-assembly of the desired molecules [ 3 , 4 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structure, and Supramolecular Understanding of 1,3,5-Tris(1-phenyl-1H-pyrazol-5-yl)benzenes

et al. 2017

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Understanding the supramolecular environment of crystal structures is necessary to facilitate designing molecules with desirable properties. A series of 12 novel 1,3,5-tris(1-phenyl-1H-pyrazol-5-yl)benzenes was used to assess the existence of planar stacking columns in supramolecular structures of pyrazoles. This class of molecules with different substituents may assist in understanding how small structural changes affect the supramolecular environment. The obtained compounds did not present the formation of planar stacking interactions between benzenes in solid or liquid states. This supposition was indicated by single crystal diffraction, Density Functional Theory (DFT) and quantum theory of atoms in molecules (QTAIM) calculations, and concentration-dependent liquid-state 1H nuclear magnetic resonance (NMR). NMR showed that chemical shifts of benzene and pyrazole hydrogens confirm that planar stacking interactions are not formed in solution. The crystalline structures presented different molecular conformations. The molecular structures of 5 and 9b are in a twisted conformation, while compound 7 showed a conformation analogous to a calyx form.

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Competition between the donor and acceptor hydrogen bonds of the threads in the formation of [2]rotaxanes by clipping reaction

Abstract: The steric effect of thet-butyl group of 1′5′-thread prevents the formation of [2]rotaxane. On the other hand, the 1′3′-thread acts a template to obtain [2]rotaxanes.

Cited by 13 publications

References 50 publications

[2]Rotaxanes Bearing a Tetralactam Macrocycle: The Role of a Trifurcated Hydrogen Bond in the Crystalline State

[2]Rotaxanes Bearing a Tetralactam Macrocycle: The Role of a Trifurcated Hydrogen Bond in the Crystalline State

Packing and Conformational Polymorphism in 1,2-Bis(aminocarbonyl(1-tert-butyl-1H-pyrazol-(3)5-yl))ethanes: Illuminating Examples of Highly Flexible Molecules

Synthesis, Crystal Structure, and Supramolecular Understanding of 1,3,5-Tris(1-phenyl-1H-pyrazol-5-yl)benzenes

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