Rotaxanos – Interações Intercomponentes E Movimentos Moleculares

Farias, Fellipe Freire Santos de; Orlando, Tainára; Salbego, Paulo R. S.; Martins, Marcos A. P.

doi:10.21577/0100-4042.20170623

Cited by 3 publications

(7 citation statements)

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“…In the hydrogen-bonded [2]rotaxane, the trifurcated hydrogen bond plays the primary role in intercomponent stabilization energy. [12][13][14]31 Other interactions that are also important for these These interactions' distributions for each portion of the rotaxane show the same pattern for all analyzed phases (Figure 6). The interactions between the station (succinamide) and macrocycle were fragmented into trifurcated hydrogen bonds and other interactions.…”

Section: ■ Experimental Sectionmentioning

confidence: 68%

“…14 All of the rotaxanes presented a mixture of rotamers (Z,Z, Z,E, and E,E) related to the slow rotation of the amide bonds in the thread. The yield obtained ranged from 14 to 59%, and all compounds were characterized by 1 H and 13 C NMR, high-resolution mass spectrometry (HRMS), and melting point (see the Supporting Information, SI for further details).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…1 H-and 13 C NMR spectra were recorded on a Bruker Avance 400 MHz instrument. 1 H NMR chemical shifts are reported relative to Me 4 Si and were referenced via residual proton resonances of the corresponding deuterated solvent, whereas 13 C NMR spectra are reported relative to Me 4 Si using the carbon signals of the deuterated solvent. Signals in the 1 H and 13 C NMR spectra of the synthesized compounds were assigned with the aid of DEPT and bidimensional experiments (COSY).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…1 H NMR chemical shifts are reported relative to Me 4 Si and were referenced via residual proton resonances of the corresponding deuterated solvent, whereas 13 C NMR spectra are reported relative to Me 4 Si using the carbon signals of the deuterated solvent. Signals in the 1 H and 13 C NMR spectra of the synthesized compounds were assigned with the aid of DEPT and bidimensional experiments (COSY). Abbreviations of coupling patterns are as follows: br, broad; s, singlet; d, doublet; t, triplet; q, quadruplet; m, multiplet.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Mechanically interlocked molecules (MIMs) have the connection between components through a mechanical bond as their main feature . The ability of one component to move in relation to the other is widely studied, mainly in solution , but also in the solid state, , conferring the possibility for acting as molecular machine prototypes. , Intercomponent interactions are directly related to these molecules’ intrinsic properties and internal movements, being studied in solution and the crystalline solid state. − Therefore, a comprehensive description of all noncovalent interactions between the interlocked components is a well-desired approach. , …”

Section: Introductionmentioning

confidence: 99%

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Mechanical Bonding as a Promoter of Crystalline Diversity in Halogenated [2]Rotaxanes

Orlando

Perez

Farias

et al. 2023

Crystal Growth & Design

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Understanding the nature of the mechanical bond is critical to advancing the design of novel mechanically interlocked molecules. Given that numerous applications of new materials are related to solid-state properties, the behavior of the mechanical bond in the crystalline solid state is a key issue to be explored. Hence, this study sought to address how the freedom degree of the interlocked components can promote the formation of different crystalline phases. A series of rotaxanes substituted with different halogen atoms in the same position of the macrocycle were chosen as the model for study. Crystallization experiments were carried out in different solvents, obtaining 15 crystalline phases for the five studied compounds. The intercomponent interactions were evaluated in solution through variable-temperature 1 H NMR experiments and in the crystalline solid state through quantum mechanics calculations. All rotaxanes presented the same type of interaction in solution and the solid state, although the distribution of interaction energies was modified depending on the crystalline phase. Selecting the substituent at the macrocycle and using different crystallization solvents at different temperatures formed these different crystalline phases. At the supramolecular crystalline level, four similar comparisons were found correlating the different compounds, in which one was the anhydrous phase and the other three phases were solvates of chloroform, tetrahydrofuran, and toluene. The key to understanding the formation of the different crystalline forms is the presence of the mechanical bond, providing the flexibility and mobility of the entwined components for keeping the most favorable intermolecular interactions in each experimental condition assayed.

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