刺激响应结晶智能材料：从理性设计和制造到应用,Accounts of Chemical Research

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刺激响应结晶智能材料：从理性设计和制造到应用
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2022-03-16 , DOI: 10.1021/acs.accounts.2c00027
Dong Yan ₁ , Zhifang Wang ₁ , Zhenjie Zhang ₁

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刺激响应智能材料在机械应力、热、光、气体、电和pH等外部刺激下可发生可逆的化学/物理变化，目前在传感器、执行器、光电器件、信息存储等领域受到越来越多的关注。、医疗应用等。目前的智能材料主要集中在聚合物、碳材料、结晶液体和水凝胶，它们没有或结构有序（即响应基团/部分在结构中无序），不可避免地引入响应速度相对较低等缺陷，能量转换效率低下，结构-性能关系不明确。所以，具有明确和规则分子阵列的晶体材料可以提供新的机会来创造具有改进的刺激响应性能的新型智能材料。晶体材料包括框架材料（如金属有机框架，MOF；共价有机框架，COF）和分子晶体（如有机分子和分子笼），与非晶材料相比，它们作为智能材料具有明显的优势。例如，响应基团/部分可以均匀地安装在晶体材料的骨架中，形成有序的分子阵列，使外部刺激信号和响应位点之间的能量传递更快、更有效。除此之外，明确的结构有助于通过原位光谱和单晶/粉末X射线衍射等各种技术和高科技设备在分子水平上原位表征其结构转变，从而有助于研究和理解刺激响应行为和结构-性质关系背后的机制。然而，晶体智能材料（CSM）仍然存在一些未解决的挑战，阻碍了智能材料系统的实际应用。例如，随着材料结晶度的增加，它们的加工性能和机械性能通常会下降，不可避免地会阻碍它们的实际应用。此外，结晶智能材料大多以微/纳米粉末形式存在，在宏观尺度上很难对刺激做出反应。因此，开发能够平衡材料结晶度和可加工性的策略并建立宏观智能材料系统对于实际应用具有重要意义。

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Stimuli-Responsive Crystalline Smart Materials: From Rational Design and Fabrication to Applications

Stimuli-responsive smart materials that can undergo reversible chemical/physical changes under external stimuli such as mechanical stress, heat, light, gas, electricity, and pH, are currently attracting increasing attention in the fields of sensors, actuators, optoelectronic devices, information storage, medical applications, and so forth. The current smart materials mostly concentrate on polymers, carbon materials, crystalline liquids, and hydrogels, which have no or low structural order (i.e., the responsive groups/moieties are disorderly in the structures), inevitably introducing deficiencies such as a relatively low response speeds, energy transformation inefficiencies, and unclear structure–property relationships. Consequently, crystalline materials with well-defined and regular molecular arrays can offer a new opportunity to create novel smart materials with improved stimuli-responsive performance. Crystalline materials include framework materials (e.g., metal–organic frameworks, MOFs; covalent organic frameworks, COFs) and molecular crystals (e.g., organic molecules and molecular cages), which have obvious advantages as smart materials compared to amorphous materials. For example, responsive groups/moieties can be uniformly installed in the skeleton of the crystal materials to form ordered molecular arrays, making energy transfer between external-stimulus signals and responsive sites much faster and more efficiently. Besides that, the well-defined structures facilitate in situ characterization of their structural transformation at the molecular level by means of various techniques and high-tech equipment such as in situ spectra and single-crystal/powder X-ray diffraction, thus benefiting the investigation and understanding of the mechanism behind the stimuli-responsive behaviors and structure–property relationships. Nevertheless, some unsolved challenges remain for crystalline smart materials (CSMs), hampering the fabrication of smart material systems for practical applications. For instance, as the materials’ crystallinity increases, their processability and mechanical properties usually decrease, unavoidably hindering their practical application. Moreover, crystalline smart materials mostly exist as micro/nanosized powders, which are difficult to make stimuli-responsive on the macroscale. Thus, developing strategies that can balance the materials’ crystallinity and processability and establishing macroscale smart material systems are of great significance for practical applications.

更新日期：2022-03-16

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