X-ray and UV Dual Photochromism, Thermochromism, Electrochromism, and Amine-Selective Chemochromism in an Anderson-like Zn₇ Cluster-Based 7-Fold Interpenetrated Framework

Smart materials are highly desirable over the recent decade due to the growing demand of complicated nature. Stable stimuli-responsive smart materials exhibit widespread potential for applications in smart windows, sensors, separators, chemical valves, and release platforms but are rare. Despite being good candidates, viologen-based multifunctional smart materials are still a challenging task for chemists. To obtain such materials, the judicious strategy is to introduce polynuclear metal-carboxylate clusters as electron donors into a stable framework to increase chromic sensitivity. Toward this endeavor, we have synthesized a novel viologen-based polymer with a unique Anderson-like metal-carboxylate cluster, [Zn₇(bpybc)₃(o-BDC)₆]·2NO₃·6H₂O (bpybc = 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium, o-BDC = <i>o</i>-benzenedicarboylic acid) (<b>1</b>), which is a particular 7-fold interpenetrated framework with a 3D <b>pcu</b> network in which bpybc ligand as the linker and Zn₇O₃₀C₁₂ as the second building unit (Zn₇ SBU) were used as 6-connected nodes. More importantly, it shows excellent chromic behavior in response to multiple external stimuli especially soft X-ray and UV dual light, temperature, electricity, and organic amines, which stand out in the viologen-based polymers. Interestingly, the coloration process of <b>1</b> from "core" to "edge" is observed upon heating at the appropriate temperature, which has not yet been found in other reported thermochromic materials. Of particular interest for <b>1</b> is the couple of quaternary stimuli-sensitive abilities because it simultaneously meets the following conditions: (i) the capability of withstanding high light, higher temperature, extreme pH, and other harsh conditions; and (ii) the high sensitivity to external stimuli keeping away from photodegradation, thermal relaxation, side reactions, and so on. To be noted, <b>1</b> has high thermal stability and chemical stability, which are excellent advantages as smart materials. To further develop possible practical utilization, <b>1</b> has been doped into the polymer matrixes to construct a hybrid film, which not only keeps the response to external stimuli but also significantly improves the repeatability of the photochromic process, indicating that a new smart device with multi-stimuli-responsive functions will emerge successively in the future.