Visible Light-Induced Collapse of Molecular Microcrystals into Droplets by E-to-Z Photoisomerization and Melting Phase Transition  

作　　者：Tian-Yi Xu Min Cui Chengxi Zhao Shang-Wu Zhou Tian-Le Zhang Hui-Yao Lin Fei Tong Da-Hui Qu 

机构地区：[1]Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center,School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237

出　　处：《CCS Chemistry》2024年第4期1071-1084,共14页中国化学会会刊（英文）

基　　金：supported by the National Natural Science Foundation of China(grant nos.22105071,22220102004,22025503,and 22335004);the Shanghai Municipal Science and Technology Major Project(grant no.2018SHZDZX03);the Innovation Program of Shanghai Municipal Education Commission(2023ZKZD40);the Fundamental Research Funds for the Central Universities,the Programme of Introducing Talents of Discipline to Universities(grant no.B16017);the Science and Technology Commission of Shanghai Municipality(grant nos.21JC1401700 and 22ZR1417100);the Shanghai Sailing Program(21YF1409200);the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(grant no.SN-ZJU-SIAS-006);C.Z.gratefully acknowledges the financial support from the China Scholarship Council(202106745008).

摘　　要：Harnessing photoresponsive behavior in organic crystals,such as shape and morphology deformation,on multiple scales is intriguing with respect to precise spatiotemporal operation,because dynamic deformations are promising in fabricating future intelligent devices.Here,we synthesized a new photoresponsive molecular crystal composed of dimethyl(E)-2-(3-(naphthalen-1-yl)allylidene)malonate((E)-DNAM)that undergoes E-to-Z photoisomerization accompanied by photoinduced crystal-to-liquid melting phase transition when exposed to visible light.Instead of expanding in bulk polycrystals,single-crystal(E)-DNAM rectangular microplates in an aqueous solution rapidly collapsed into liquid droplets,showing a remarkable drastic reduction in surface area of more than 97%after light illumination.We deduce that the unique microscopic morphology of microplates with high aspect ratios of length-tothickness reaching up to 1000 is mainly responsible for the photoinduced melting leading to drastic collapse.In addition,the cohesive forces of liquid photoproduct facilitate the overall deformations and transformation.We have shown a facile way to achieve the remarkable collapse of molecular crystals into droplets by photochemical reaction and phase transition.

关 键 词：molecular crystals crystal-to-liquid transition extreme deformations PHOTOCHEMISTRY crystal engineering flexible crystals 

分 类 号：O62[理学—有机化学]