摘要
近年来,高压越来越多地被当作一种诱导化学反应的方式,应用于丁二炔聚合反应、乙炔聚合反应、异氰酸酯的聚合反应等。高压诱导新反应的开发,对于绿色化学反应及新型晶体中化学反应的开发具有指导意义。我们课题组借助于金刚石对顶砧技术提供的高压和原位检测手段,实现了高压诱导螺吡喃的异构化反应~([1]),这一过程主要是由于螺吡喃异构化过程中反应体积的减小导致的。该过程可通过肉眼观察到,进而有望实现高压诱导的化学反应应用于高压检测、高压传感材料中。为了进一步提高该压致变色过程的灵敏性,实现具有多重响应的多色压致变色过程,我们将力诱导的化学反应与力诱导非共价相互作用变化结合,借助于二者强度的差别,较低压力下的非共价相互作用变化实现荧光发射的可逆变化,而较高压力诱导的化学反应实现了荧光发射的不可逆变化,实现了可调控的高压下力致多色转变。该策略还可以应用于其他压致多色转变分子的制备。
Pressure, as one of the most common natural external stimuli, has been gradually applied in syntheses, especially in organic syntheses in solid state. Recently, the visible isomerization of spiropyrans in crystals was realized under high pressure by our group. In order to further improve the sensitivity of the responses and realize multi-colored switching, other mechanophores based on supramolecular changes under pressure were induced. Benefitting from the combination of supramolecular and chemical structural changes, the high pressure achieved by the Diamond Anvil Cell technique induced a continuous mechanochromic process involving a color change from blue to red emission. Due to the distinct strengths of covalent and non-covalent interactions, the multi-mechanochromic properties could be modulated by the strength of the external force. These molecules have great potentials for the applications in pressure sensors, pressure calibration, and mechanoprobes.
引文
[1]Meng,X.;Qi,G.;Zhang,C.;Wang,K.;Zou,B.;Ma,Y.Chem.Commum.2015,51:9320.