Flexible hydrogen-bonded organic frameworks (FHOFs) have attracted great attention due to their unique dynamics and versatile applications; however, designing FHOFs remains a challenge. Herein, we report the first example of a flexible HOF (named 8PZ) with local dynamics for adaptive guest accommodation through incorporating soft ethyl-ester chains. Single-crystal X-ray diffraction (SXRD) analyses reveal that, in response to various external stimuli, local motions of ethyl-ester chains occur with unaltered molecular assembling forms of 8PZ, which can efficiently regulate pore sizes but allow for stable luminescence performances. 8PZ can adapt to a series of 3-alkylthiophenes with large-scale alkyl-chain-length variation through its local dynamics. Host-guest cocrystals amenable to SXRD analyses are produced, which present programmable temperature-dependent luminescence behaviors and show potential for various crucial applications. This work provides a promising avenue to engineer future multifunctional HOFs, thus enriching the types and applications of existing porous materials.

柔性氢键有机框架（FHOFs）由于其独特的动力学和广泛的应用而引起了极大的关注；然而，设计 FHOF 仍然是一个挑战。在此，我们报告了第一个灵活的 HOF（命名为 8PZ）的例子，它通过结合软乙酯链具有适应性客人住宿的局部动力学。单晶 X 射线衍射 (SXRD) 分析表明，为了响应各种外部刺激，乙酯链的局部运动发生在 8PZ 的分子组装形式不变的情况下，它可以有效地调节孔径，同时实现稳定的发光性能。8PZ可以通过其局部动力学适应一系列具有大规模烷基链长度变化的3-烷基噻吩。产生了适合 SXRD 分析的主客体共晶，它呈现出可编程的温度依赖性发光行为，并显示出各种关键应用的潜力。这项工作为设计未来的多功能 HOFs 提供了一条有前途的途径，从而丰富了现有多孔材料的类型和应用。