通过烷基官能化的框架材料调控SP@Tb-MOFs的动态荧光材料性能并探究其在时间分辨信息加密中的应用  

Boosting dynamic fluorescent materials using SP@Tb-MOFs through the alkyl functionalization of pores and applications in time-dependent information encryption

作　　者：朱姜昆 卫尤豪 高阳旸 倪骅程 蔡海涛 武聪浩 杨玉慧 Jiangkun Zhu;Youhao Wei;Yangyang Gao;Huacheng Ni;Haitao Cai;Conghao Wu;Yuhui Yang(School of Materials Science and Engineering,Zhejiang Sci-Tech University,Hangzhou 310018,China;Department of Polymer Materials,Zhejiang Sci-Tech University,Hangzhou 310018,China;Institute of Smart Biomedical Materials,Zhejiang Sci-Tech University,Hangzhou 310018,China)

机构地区：[1]School of Materials Science and Engineering,Zhejiang Sci-Tech University,Hangzhou 310018,China [2]Department of Polymer Materials,Zhejiang Sci-Tech University,Hangzhou 310018,China [3]Institute of Smart Biomedical Materials,Zhejiang Sci-Tech University,Hangzhou 310018,China

出　　处：《Science China Materials》2024年第8期2590-2599,共10页中国科学（材料科学）（英文版）

基　　金：supported by the Zhejiang Sci-Tech University Shengzhou Innovation Research Institute(SYY2.023C000005);the National Natural Science Foundation of China(51803184)。

摘　　要：动态荧光材料在数据存储和防伪技术领域受到广泛关注.在此,我们提出了一种得到动态荧光材料的新方法,即在烷基链修饰的镧系金属有机框架(Ln-MOFs)中引入螺吡喃(SP)分子.烷基化配体既可用作桥接配体,也可用作结构导向剂,以调节镧系金属有机框架的形态.通过控制烷基链的长度,可以调整Tb-MOFs的形态,从而进一步调节复合体系的光致变色行为.当烷基链较短时,复合体系只能发出黄色或者绿色的光.只有SP@Tb-MOF-10C能在545 nm波长处发出Tb^(3+)的绿色发射,在650 nm波长处发出SP的红色发射.在365 nm紫外光的持续照射下,SP分子发生了光异构化过程,变成了开环形式,从而导致Tb-MOF与其光异构体(MC)之间发生了显著的荧光共振能量转移(FRET).在白光照射下,这些复合材料的动态荧光行为可完全恢复到初始状态.此外,本文通过将该复合体系掺杂聚二甲基硅氧烷(PDMS),制备了复合薄膜,并探究了其在防伪标签和时间分辨动态加密方面的应用.Dynamic fluorescent materials have received widespread attention in the fields of data storage and anticounterfeiting technology.Here,we present a new approach to achieving dynamic fluorescent materials by introducing spiropyran(SP)molecules into alkyl-chain-modified lanthanide metal-organic frameworks(Ln-MOFs).Alkylated ligands can serve as both bridging ligands and structural directors to regulate the morphology of Tb-MOFs.By controlling the length of the alkyl chain,the morphology of Tb-MOFs was adjusted,thus further regulating the photochromic behaviors of the composite system.When the alkyl chain is short,the composite system emits yellow or even green emissions.Only SP@Tb-MOF-10C shows the green emission of Tb^(3+)at 545 nm and the red emission of SP at 650 nm.Under continuous irradiation of 365 nm ultraviolet(UV)light,SP molecules underwent a photoisomerization process to the open-ring form,leading to a significant fluorescence resonance energy transfer between Tb-MOF and its isomer merocyanine(MC).These composites exhibit dynamic fluorescence behavior and can be fully restored to their initial states when exposed to white light.In addition,a composite film was prepared by doping with polydimethylsiloxane(PDMS).Its applications in anticounterfeiting labels and time-resolved dynamic encryption were demonstrated.

关 键 词：信息加密 防伪标签 金属有机框架 荧光材料 动态加密 光异构化 防伪技术 时间分辨 

分 类 号：TP309.7[自动化与计算机技术—计算机系统结构] O641.4[自动化与计算机技术—计算机科学与技术] TB34[理学—物理化学]