Cold crystallization in the mixed system of adenine and thymine dodecyl derivatives

Kimijima, Ayaka; Honda, Akinori; Nomoto, K.; Miyamura, Kazuo

doi:10.1039/c9ce00407f

Cited by 12 publications

(21 citation statements)

References 21 publications

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“…Most materials that exhibit cold crystallization have a slow rate of crystallization from the liquid to the solid phase. Previous studies have typically investigated polymeric materials, − but recent research has focused on smaller molecular materials, such as ionic liquids, , liquid crystals, − organic materials, ,− and metal complexes. ,− Most of these studies focus on the thermal behavior of these materials (e.g., macroscopic heat absorption and emission), and only a few studies have investigated the molecular structural features associated with such thermal behavior or presented guidelines for designing molecules applicable for thermal energy storage. ,,, …”

Section: Introductionmentioning

confidence: 99%

Cold Crystallization and the Molecular Structure of Imidazolium-Based Ionic Liquid Crystals with a p-Nitroazobenzene Moiety

et al. 2021

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The cold crystallization mechanism of 1-{[4′-(4″-nitrophenylazo)phenyloxy]}hexyl-3-methyl-1H-imidazol-3-ium tetrafluoroborate ionic liquid crystal was investigated based on thermal analysis, structural analysis, infrared spectroscopy, and quantum chemical calculations. By conducting thorough structural characterization, we found that the prerequisite for cold crystallization is the irreversible molecular conformational alteration induced by the initial heating of the as-grown crystal into a smectic liquid crystal. The originally linear cation molecule bends and forms a step-stair conformation that persists throughout the subsequent heating and cooling processes as phase transition occurs from the crystal phase to the liquid crystal phase and then to the isotropic liquid phase. The formation of cold crystal occurs because of the choice of molecular stability over crystalline stability. Given the exothermic anomaly exhibited upon heating generic crystals to cold crystals, these findings demonstrate the promising potential of this ionic liquid crystal for thermal energy storage applications.

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Section: Introductionmentioning

confidence: 99%

Cold Crystallization and the Molecular Structure of Imidazolium-Based Ionic Liquid Crystals with a p-Nitroazobenzene Moiety

et al. 2021

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“…This cold crystallization behavior is most commonly observed in macromolecular systems. Several examples of small molecules exhibiting cold crystallization have been reported; however, these small molecules typically are substituted with extended alkyl chains to discourage the molecular ordering required for crystallization [28–33] . Cold crystallization has been previously noted in DES systems [31, 34] .…”

Section: Resultsmentioning

confidence: 99%

“…This behavior is reproducible during the 2 nd cooling/heating process.T his cold crystallization behavior is most commonly observed in macromolecular systems.S everal examples of small molecules exhibiting cold crystallization have been reported;h owever, these small molecules typically are substituted with extended alkyl chains to discourage the molecular ordering required for crystallization. [28][29][30][31][32][33] Cold crystallization has been previously noted in DES systems. [31,34] Unfortunately,a ll attempts to further characterize these phase transitions via powder XRD were unsuccessful.…”

Section: Methodsmentioning

confidence: 93%

Halogen Bonding in Dithiane/Iodofluorobenzene Mixtures: A New Class of Hydrophobic Deep Eutectic Solvents

et al. 2021

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While research into deep eutectic solvents (DESs) has expanded over the previous two decades, the focus has remained on the utilization of hydrogen bond donors in these systems. Additionally, the majority of the known DESs rely on at least one ionic component. Through the combination of 1,3‐dithiane and 1,2‐diiodo‐3,4,5,6‐tetrafluorobenzene (1,2‐F4DIB), we report the first known DES based on halogen bonding. This mixture remains a liquid, with a eutectic melting temperature of 13.7 °C over a range of 1,3‐dithiane mole fraction (0.35 to 0.75). Additionally, cocrystals of 1,3‐ and 1,4‐dithiane with 1,2‐, 1,3‐, and 1,4‐F4DIB, as well as 1,3,5‐trifluoro‐2,4,6‐triiodobenzene were studied via single‐crystal X‐ray diffraction. These data reveal a wide range of halogen bonding strengths (0.85

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“…12,13 These molecules form amorphous phases upon cooling from the isotropic liquid, and the stability of the amorphous phase can be controlled by the position of the substituents. Recent examples include flexible dendrimers with a number of alkyl chains, 14 metallocomplexes with conformationally isomeric ligands, 15 multiple hydrogen-bonding molecules, 16,17 and the butterfly shaped tetrabenzofluorene derivative. 18 We have focused on the rotational flexibilitya limited structural freedomof ferrocene (Fc) and designed Fc derivatives having conjugated molecular units at their 1,1′positions.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Some of the most famous small molecular materials showing cold crystallization are triarylamine derivatives with unsymmetric functional groups. , These molecules form amorphous phases upon cooling from the isotropic liquid, and the stability of the amorphous phase can be controlled by the position of the substituents. Recent examples include flexible dendrimers with a number of alkyl chains, metallocomplexes with conformationally isomeric ligands, multiple hydrogen-bonding molecules, , and the butterfly shaped tetrabenzofluorene derivative …”

Section: Introductionmentioning

confidence: 99%

Cold Crystallization of Ferrocene-Hinged π-Conjugated Molecule Induced by the Limited Conformational Freedom of Ferrocene

et al. 2019

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Crystallization that proceeds above the glass transition temperature upon heating the glassy or amorphous state is referred to as "cold crystallization", which has often been observed in supercooled phases of molecular materials followed by the transition to the thermodynamically stable crystalline phase. Although this behavior is common for the macromolecules with high structural flexibility among segments preserving the wide temperature range of corresponding glassy phases, cold crystallization of small molecules is relatively rare and there is still less knowledge on the design guideline of such molecules. Here we report a ferrocenehinged molecule D C12 carrying two units of didodecylsubstituted pentathiophenes at the 1,1′-positions. Due to the rotational freedom of the ferrocene unit, D C12 forms amorphous solid on cooling from its isotropic melt. The amorphous state was realized even by slow cooling such as 0.1 °C min −1 . The possible reason for the easy formation of the amorphous phase is the coexistence of various conformations of D C12 originating from the open conformers of the ferrocene. On heating from the amorphous phase, D C12 shows cold crystallization with the estimated activation energy of 61 kJ mol −1 . The crystalline phase is composed of the closed form of D C12 molecules packed in a lamellar fashion, and the degree of crystallinity is remarkably high compared with the case of macromolecular materials. The crystallization is triggered by the intermolecular interactions among the dodecyl chains and rotational flexibility of the ferrocene unit. This work provides an unprecedented example that ferrocenes act as heat-controllable rotational hinges in condensed phases. Considering that the cold crystallization phenomenon is related to heat-storage materials, the design strategy presented in this work will be novel to realize both easily formed amorphous phases and highly crystalline phases formed through cold crystallization.

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Cold crystallization in the mixed system of adenine and thymine dodecyl derivatives

Abstract: The 1 : 1 mixture of adenine and thymine both substituted with dodecyl groups exhibited the unique thermal behavior.

Cited by 12 publications

References 21 publications

Cold Crystallization and the Molecular Structure of Imidazolium-Based Ionic Liquid Crystals with a p-Nitroazobenzene Moiety

Cold Crystallization and the Molecular Structure of Imidazolium-Based Ionic Liquid Crystals with a p-Nitroazobenzene Moiety

Halogen Bonding in Dithiane/Iodofluorobenzene Mixtures: A New Class of Hydrophobic Deep Eutectic Solvents

Cold Crystallization of Ferrocene-Hinged π-Conjugated Molecule Induced by the Limited Conformational Freedom of Ferrocene

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