Crystallization Kinetics of a Liquid-Forming 2D Coordination Polymer

We investigated a mechanism of crystal melting and crystallization behavior of a two-dimensional coordination polymer [Ag2(L1)­(CF3SO3)2] (1, L1 = 4,4′-biphenyldicarbonitrile) upon heating-cooling processes. The crystal showed melting at 282 °C, and the following gentle cooling induced the abrupt cr...

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Published inNano letters Vol. 22; no. 23; pp. 9372 - 9379
Main Authors Das, Chinmoy, Nishiguchi, Taichi, Fan, Zeyu, Horike, Satoshi
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 14.12.2022
Subjects
Calorimetry, Differential Scanning
Crystallization
Kinetics
Phase Transition
Polymers - chemistry
Glasses
Coordination polymers
Metal−organic frameworks
Crystal melting
Crystallization
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Abstract We investigated a mechanism of crystal melting and crystallization behavior of a two-dimensional coordination polymer [Ag2(L1)­(CF3SO3)2] (1, L1 = 4,4′-biphenyldicarbonitrile) upon heating-cooling processes. The crystal showed melting at 282 °C, and the following gentle cooling induced the abrupt crystallization at 242 °C confirmed by DSC. A temperature-dependent structural change has been discussed through calorimetric, spectroscopic, and mechanical measurements. They indicated that the coordination-bond networks are partially retained in the melt state, but the melt showed a significantly low viscosity of 9.8 × 10–2 Pa·s at T m which is six orders lower than that of ZIF-62 at T m (435 °C). Rheological studies provided an understanding of the fast relaxation dynamics for the recrystallization process, along with that the high T m provides enough thermal energy to crossover the activation energy barrier for the nucleation. The isothermal crystallization kinetics through calorimetric measurements with applying the Avrami equation identified the nature of the nuclei and its crystal growth mechanism.
AbstractList We investigated a mechanism of crystal melting and crystallization behavior of a two-dimensional coordination polymer [Ag2(L1)(CF3SO3)2] (1, L1 = 4,4'-biphenyldicarbonitrile) upon heating-cooling processes. The crystal showed melting at 282 °C, and the following gentle cooling induced the abrupt crystallization at 242 °C confirmed by DSC. A temperature-dependent structural change has been discussed through calorimetric, spectroscopic, and mechanical measurements. They indicated that the coordination-bond networks are partially retained in the melt state, but the melt showed a significantly low viscosity of 9.8 × 10-2 Pa·s at Tm which is six orders lower than that of ZIF-62 at Tm (435 °C). Rheological studies provided an understanding of the fast relaxation dynamics for the recrystallization process, along with that the high Tm provides enough thermal energy to crossover the activation energy barrier for the nucleation. The isothermal crystallization kinetics through calorimetric measurements with applying the Avrami equation identified the nature of the nuclei and its crystal growth mechanism.We investigated a mechanism of crystal melting and crystallization behavior of a two-dimensional coordination polymer [Ag2(L1)(CF3SO3)2] (1, L1 = 4,4'-biphenyldicarbonitrile) upon heating-cooling processes. The crystal showed melting at 282 °C, and the following gentle cooling induced the abrupt crystallization at 242 °C confirmed by DSC. A temperature-dependent structural change has been discussed through calorimetric, spectroscopic, and mechanical measurements. They indicated that the coordination-bond networks are partially retained in the melt state, but the melt showed a significantly low viscosity of 9.8 × 10-2 Pa·s at Tm which is six orders lower than that of ZIF-62 at Tm (435 °C). Rheological studies provided an understanding of the fast relaxation dynamics for the recrystallization process, along with that the high Tm provides enough thermal energy to crossover the activation energy barrier for the nucleation. The isothermal crystallization kinetics through calorimetric measurements with applying the Avrami equation identified the nature of the nuclei and its crystal growth mechanism.
We investigated a mechanism of crystal melting and crystallization behavior of a two-dimensional coordination polymer [Ag2(L1)­(CF3SO3)2] (1, L1 = 4,4′-biphenyldicarbonitrile) upon heating-cooling processes. The crystal showed melting at 282 °C, and the following gentle cooling induced the abrupt crystallization at 242 °C confirmed by DSC. A temperature-dependent structural change has been discussed through calorimetric, spectroscopic, and mechanical measurements. They indicated that the coordination-bond networks are partially retained in the melt state, but the melt showed a significantly low viscosity of 9.8 × 10–2 Pa·s at T m which is six orders lower than that of ZIF-62 at T m (435 °C). Rheological studies provided an understanding of the fast relaxation dynamics for the recrystallization process, along with that the high T m provides enough thermal energy to crossover the activation energy barrier for the nucleation. The isothermal crystallization kinetics through calorimetric measurements with applying the Avrami equation identified the nature of the nuclei and its crystal growth mechanism.
We investigated a mechanism of crystal melting and crystallization behavior of a two-dimensional coordination polymer [Ag (L1)(CF SO ) ] ( , L1 = 4,4'-biphenyldicarbonitrile) upon heating-cooling processes. The crystal showed melting at 282 °C, and the following gentle cooling induced the abrupt crystallization at 242 °C confirmed by DSC. A temperature-dependent structural change has been discussed through calorimetric, spectroscopic, and mechanical measurements. They indicated that the coordination-bond networks are partially retained in the melt state, but the melt showed a significantly low viscosity of 9.8 × 10 Pa·s at which is six orders lower than that of ZIF-62 at (435 °C). Rheological studies provided an understanding of the fast relaxation dynamics for the recrystallization process, along with that the high provides enough thermal energy to crossover the activation energy barrier for the nucleation. The isothermal crystallization kinetics through calorimetric measurements with applying the Avrami equation identified the nature of the nuclei and its crystal growth mechanism.
Author Das, Chinmoy
Nishiguchi, Taichi
Fan, Zeyu
Horike, Satoshi
AuthorAffiliation Kyoto University
Institute for Integrated Cell-Material Sciences, Institute for Advanced Study
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering
Department of Materials Science and Engineering, School of Molecular Science and Engineering
Vidyasirimedhi Institute of Science and Technology
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  email: horike@icems.kyoto-u.ac.jp
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Coordination polymers
Metal−organic frameworks
Crystal melting
Crystallization
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Snippet We investigated a mechanism of crystal melting and crystallization behavior of a two-dimensional coordination polymer [Ag2(L1)­(CF3SO3)2] (1, L1 =...
We investigated a mechanism of crystal melting and crystallization behavior of a two-dimensional coordination polymer [Ag (L1)(CF SO ) ] ( , L1 =...
We investigated a mechanism of crystal melting and crystallization behavior of a two-dimensional coordination polymer [Ag2(L1)(CF3SO3)2] (1, L1 =...
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SubjectTerms Calorimetry, Differential Scanning
Crystallization
Kinetics
Phase Transition
Polymers - chemistry
Title Crystallization Kinetics of a Liquid-Forming 2D Coordination Polymer
URI http://dx.doi.org/10.1021/acs.nanolett.2c03207
https://www.ncbi.nlm.nih.gov/pubmed/36441580
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