Arylazopyrazole-functionalized photoswitchable octanuclear Zn(Ⅱ)-silsesquioxane nanocage  

作　　者：Kai Sheng Ya-Nan Liu Rakesh Kumar Gupta Mohamedally Kurmoo Di Sun 

机构地区：[1]School of Aeronautics,Shandong Jiaotong University,Ji'nan 250037,China [2]School of Chemistry and Chemical Engineering,State Key Laboratory of Crystal Materials,Shandong University,Ji'nan 250100,China [3]Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology,School of Chemistry and Chemical Engineering,厶iaocheng University,Liaocheng 252000,China [4]Institut de Chimie de Strasbourg,Universite de Strasbourg,CNRS-L/MR 7177,4 rue Blaise Pascal,Strasbourg Cedex 67008,France

出　　处：《Science China Chemistry》2021年第3期419-425,共7页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(91961105,21822107,21571115,21827801);the Natural Science Foundation of Shandong Province(ZR2019ZD45,JQ201803,ZR2017MB061);the Taishan Scholar Project of Shandong Province of China(tsqn201812003,ts20190908);the Qilu Youth Scholar Funding of Shandong University;the Project for Scientific Research Innovation Team of Young Scholar in Colleges and Universities of Shandong Province(2019KJC028,2019KJJ009);the State Key Laboratory of Pollution Control and Resource Reuse Foundation(PCRRF18019)。

摘　　要：Photoswitchable organic materials have shown significant advancement for photonic applications,however,the polynuclear metal clusters conjugated with photoswitching properties are still formidable.Herein,a novel octanuclear Zn(Ⅱ) nanocage{[Zn_(8)-(Me_(4)Si_(4)O_(8))_(2)(azopz)_(8)]·4CH_(2)Cl_(2)·MeOH·MeCN}(SD/Zn8)(Hazopz=3,5-dimethyl-4-(phenyldiazenyl)-1H-pyrazole),based on multidentate silsesquioxane and pyrazole modified by photoisomerizable azo group has been designed and synthesized to realize the reversible photoswitching behavior.X-ray crystallographic study reveals that the unique metal core consists of two annular Me_(4)Si_(4)O_(8)^(4-)sandwiching a ring of eight Zn atoms where the pyrazole end of azopz-bridges them together.The azopz-ligands diverge above and below the plane defined by eight Zn atoms.Importantly,SD/Zn8 shows quick trans-to-cis transformation upon 365 nm light irradiation,which can be easily changed back by 450 nm light,but slow cis-to-trans reversibility at room temperature as confirmed by UV-V is and 1H NMR spectroscopies.This process,which presumably regulates the spaces,acts like a pump and is completely repetitive.As such,it can be considered as a molecular pump energized by light.Importantly,the molecule is an energy reservoir where it absorbs the light energy and releases it slowly with time.

关 键 词：SILSESQUIOXANE metal-organic nanocage PHOTOCHROMISM X-ray single-crystal structure 

分 类 号：O641.4[理学—物理化学] TB383.1[理学—化学]