Crystallization Kinetics of a Liquid-Forming 2D Coordination Polymer,Nano Letters

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Crystallization Kinetics of a Liquid-Forming 2D Coordination Polymer
Nano Letters ( IF 9.6 ) Pub Date : 2022-11-28 , DOI: 10.1021/acs.nanolett.2c03207
Chinmoy Das ₁ , Taichi Nishiguchi ₂ , Zeyu Fan ₂ , Satoshi Horike _{1,

2,

3}

Affiliation

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.

中文翻译：

液态二维配位聚合物的结晶动力学

我们研究了二维配位聚合物 [Ag ₂ (L1)(CF ₃ SO ₃ ) ₂ ] ( 1 , L1 = 4,4'-联苯二腈) 在加热-冷却过程中的晶体熔化和结晶行为机制。晶体显示在 282 °C 熔化，随后的温和冷却诱导在 242 °C 时突然结晶，DSC 证实了这一点。通过量热、光谱和机械测量讨论了与温度相关的结构变化。他们指出，配位键网络部分保留在熔体状态下，但熔体在T _{m时显示出 9.8 × 10}^–2 Pa·s的显着低粘度在Tm (435 °C)_时比 ZIF-62 低 6 个数量级。流变学研究提供了对再结晶过程的快速弛豫动力学的理解，同时高Tm_提供了足够的热能来跨越成核的活化能垒。通过应用 Avrami 方程进行量热测量的等温结晶动力学确定了晶核的性质及其晶体生长机制。

更新日期：2022-11-28

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