Stimuli-responsive intelligent molecular machines/devices are of current research interest due to their potential application in minimized devices. Constructing molecular machines/devices capable of accomplishing complex missions is challenging, demanding coalescence of various functions into one molecule. Here we report the construction of intelligent molecular chiroptical photoswitches based on azobenzene-fused bicyclic pillar[n]arene derivatives, which we defined as molecular universal joints (MUJs). The Z/E photoisomerization of the azobenzene moiety of MUJs induces rolling in/out conformational switching of the azobenzene-bearing side-ring and consequently leads to planar chirality switching of MUJs. Meanwhile, temperature variation was demonstrated to also cause conformational/chiroptical inversion due to the significant entropy change during the ring-flipping. As a result, photo-induced chiroptical switching could be prohibited when the temperature exceeded an upper limit, demonstrating an intelligent molecular photoswitch having over-temperature protection function, which is in stark contrast to the low-temperature-gating effect commonly encountered.

响应敏感的智能分子机器/设备由于其在最小化设备中的潜在应用而引起了当前的研究兴趣。构建能够完成复杂任务的分子机器/设备具有挑战性，要求将各种功能融合为一个分子。在这里，我们报告基于偶氮苯稠合的双环支柱[ n ]芳烃衍生物的智能分子手性光开关的构建，我们将其定义为分子通用接头（MUJs）。该ž / ëMUJ的偶氮苯部分的光异构化引起带有偶氮苯的侧环的滚入/滚出构象转换，并因此导致MUJ的平面手性转换。同时，由于环翻转过程中熵的显着变化，温度变化也导致构象/手性倒位。结果，当温度超过上限时，可以禁止光致手性开关，这说明了具有过热保护功能的智能分子光开关，这与通常遇到的低温门控作用形成鲜明对比。