含脲六元螺环罗丹明对水中金属离子的光谱响应及电致变色性质研究  

A Six-membered Spirorhodamine Bearing Urea Moiety Responsing to Metal Ions and Its Electrochromic Properties in Water

作　　者：肖彦楠 梁冲 韩月 吴迪 习丽丽 于海波[1] 吕宝阔 XIAO Yannan;LIANG Chong;HAN Yue;WU Di;XI Lili;YU Haibo;LYU Baokuo(School of Environment,Liaoning University,Shenyang 110036,China;Shenyang Hydrological Bureau of Liaoning Province,Shenyang 110003,China;Liaoning Provincial River Reservoir Management Service Center(Liaoning Provincial Hydrological Bureau),Shenyang 110003,China)

机构地区：[1]辽宁大学环境学院,辽宁沈阳110036 [2]辽宁省沈阳水文局,辽宁沈阳110003 [3]辽宁省河库管理服务中心(辽宁省水文局),辽宁沈阳110003

出　　处：《发光学报》2025年第1期164-173,共10页Chinese Journal of Luminescence

基　　金：辽宁省应用基础研究计划项目(2023JH2/101300244);辽宁省一流本科课程资助(2022);兴辽计划(XLYC1907002);辽宁大学研究生优质课程建设与教学模式综合改革研究项目(YJG202301025);辽宁大学学生创新创业训练项目;辽宁大学第二批课程思政示范课程;哈尔滨工业大学城市水资源与环境国家重点实验室开放项目(ES202304)。

摘　　要：为了探究六元螺环在金属离子响应和电致变色领域的应用,本文采用一锅多步的方法成功设计制备了含氨基脲结构的六元螺环罗丹明SRh-NH,并对其进行结构表征。与五元螺环罗丹明类似,SRh-NH对酸性敏感(pH 3.0~6.0),当pH>6.0时螺环结构较为稳定,不易发生开环反应,其pKa分别为4.62(abs)和4.76(fl)。在金属离子选择性方面,Cu^(2+)和Hg^(2+)均能诱使SRh-NH发生开环反应,同时吸收光谱在566 nm处和荧光光谱在589 nm处分别出现了新的吸收峰和荧光峰。弱金属离子选择性表明SRh-NH对Cu^(2+)和Hg^(2+)识别更为灵敏,对Cu^(2+)和Hg^(2+)的检出限分别为64 nmol/L(fl)和2.7μmol/L(fl),同时其竞争性也易受到三价金属离子的干扰。此外,以SRh-NH为变色层,在施加+1.0 V和-0.8 V的电压时,薄膜颜色和荧光均可在无色和深红色之间切换。SRh-NH的构效关系表明,该六元螺环结构在六元螺环罗丹明荧光探针和电致变色荧光薄膜的设计应用中具备较大的应用潜力。In order to explore the application of six-membered spirocycles in the field of metal ion response and electroluminescence,a six-membered spiro ring rhodamine SRh-NH containing semicarbazide structure was successfully designed and prepared by a one-pot multi-step method,and its structure was characterized.Similar to the fivemembered spirocyclic rhodamine,SRh-NH is sensitive to acidity(pH 3.0-6.0).When pH>6.0,the spirocyclic structure is more stable and less prone to ring-opening reaction,and its pKa is 4.62(abs)and 4.76(fl),respectively.In terms of metal ion selectivity,both Cu^(2+)and Hg^(2+)can induce the ring-opening reaction of SRh-NH,and new absorption peaks and fluorescence peaks appear at 566 nm and 589 nm,respectively.The weak metal ion selectivity indicates that SRh-NH is more sensitive to Cu^(2+)and Hg^(2+),and the detection limits for Cu^(2+)and Hg^(2+)are 64 nmol/L(fl)and 2.7μmol/L(fl),respectively.At the same time,its competition is also susceptible to trivalent metal ions.In addition,using SRh-NH as the color-changing layer,the color and fluorescence of the film can be switched between colorless and deep red when the voltages of+1.0 V and-0.8 V are applied.The structure-activity relationship of SRh-NH indicates that the six-membered spiro ring structure has great application potential in the design and application of six-membered spiro ring rhodamine fluorescent probes and electrochromic fluorescent films.

关 键 词：六元螺环罗丹明 金属离子 电致变色 红色荧光 

分 类 号：O482.31[理学—固体物理]