Solano-Rodríguez Enrique, Sun Qi, Brédas Jean-Luc, Coropceanu Veaceslav, Jurado-Sánchez Beatriz, Escarpa Alberto
Department of Analytical Chemistry, Physical Chemistry, and Chemical Engineering, Universidad de Alcala, Alcala de Henares, Madrid, E-28802, Spain.
Department of Chemistry and Biochemistry, The University of Arizona, Tucson, Arizona, 85721-0041, USA.
Angew Chem Int Ed Engl. 2025 Aug 18;64(34):e202506269. doi: 10.1002/anie.202506269. Epub 2025 Jul 1.
Here, we describe the synthesis and photo-responsive properties of 2D cyclo-octasulfur microcrystals (α-S8 MCs), produced using a quick, simple, cost-effective, and environmentally friendly hydrothermal method. Controlled 385-nm irradiation of these crystals induces an immediate, reversible, and sustained bending effect. The time required for the crystals to return to their initial shape is significantly reduced when exposed to 475-nm light, completing the entire excitation-relaxation cycle in less than 2 s. Moreover, this process can be repeated up to 50 times as long as the crystals remain in water. The dependence of recovery time on light wavelength is rationalized qualitatively via highly correlated quantum-chemical calculations of the absorption spectra of S8 chains. The underlying mechanism involves a combination of ring-to-chain and chain-to-ring transformations: the breaking of α-S8 rings by 385-nm radiation induces bending in the α-S8 MCs, while the excitation of the chains with 475-nm light facilitates an accelerated recovery process, allowing the S8 molecules to swiftly regain their ring shape. Thus, our study demonstrates that α-S8 MCs represent intelligent actuators as light-controlled molecular muscles with the simplest inorganic composition reported to date.
在此,我们描述了使用快速、简单、经济高效且环保的水热法制备的二维环八硫微晶(α-S8微晶)的合成及光响应特性。对这些晶体进行385纳米的可控照射会引发即时、可逆且持续的弯曲效应。当暴露于475纳米光下时,晶体恢复到初始形状所需的时间会显著缩短,在不到2秒内完成整个激发 - 弛豫循环。此外,只要晶体保持在水中,这个过程可以重复多达50次。通过对S8链吸收光谱进行高度相关的量子化学计算,定性地解释了恢复时间对光波长的依赖性。其潜在机制涉及环到链和链到环转变的组合:385纳米辐射使α-S8环断裂,导致α-S8微晶弯曲,而475纳米光激发链则促进加速恢复过程,使S8分子迅速恢复其环形。因此,我们的研究表明,α-S8微晶作为迄今为止报道的具有最简单无机组成的光控分子肌肉,代表了智能致动器。