All Roads Lead to Rome: Tuning the Luminescence of a Breathing Catenated Zr-MOF by Programmable Multiplexing Pathways

A zirconium-based
metal–organic framework (Zr-MOF) with
a 2-fold catenated breathing structure is designed, whose framework
contracts in a similarly consecutive manner responsive to solvent
(S), temperature (T), or pressure
(P). As a result, photoluminescence color tuning
(PLCT) can be achieved progressively from blue to yellow, via S, T, or P pathways, leading
to multiple PL states with memory nature. Based on this, a 3D PLCT
coordinate system is established. Along each stimulation pathway,
the starting, ending, and multiple intermediate PLCT states can be
recognized and plotted on the S, T, and P axes of the coordinate system. Furthermore,
multiplexing node-transfer pathways are programmed among the axes,
in which two or three kinds of outer stimuli (S/T/P) are implemented successively and alternatively,
leading to various stages of PL states. This multiplexing approach
provides a new strategy to control and utilize the multiresponsiveness
of PL-MOFs for intriguing applications such as composite nonvolatile
data storage and so on.

本研究设计得到一种具有二重互穿呼吸型结构的锆基金属有机框架（Zr-MOF），其骨架可响应溶剂（S）、温度（T）或压力（P）刺激，以连续一致的模式发生收缩。借此，可通过溶剂、温度或压力三条调控路径，实现从蓝色到黄色的渐进式光致发光颜色调控（PLCT），获得多种具备记忆特性的光致发光状态。基于该特性，我们构建了三维光致发光颜色调控坐标系。沿每条刺激路径，可在该坐标系的S、T、P轴上分别识别并标注出起始、终止以及多种中间光致发光颜色调控状态。进一步，我们在各坐标轴之间编程设计了多路节点转移路径：依次或交替施加两种或三种外部刺激（S/T/P），可得到不同阶段的光致发光状态。该多路调控策略为调控与利用光致发光金属有机框架（PL-MOFs）的多响应特性提供了全新思路，可应用于复合非易失性数据存储等极具应用前景的场景。