取代苯甲酸根对银(Ⅰ)⁃四(4⁃吡啶基)乙烯金属有机框架材料的结构与发光性质调控  

Structure and photoluminescence modulation of silver(Ⅰ)⁃tetra(pyridin⁃4⁃yl)ethene metal⁃organic frameworks by substituted benzoates

作　　者：丁乙 廖培毓 贾建华 童明良 DING Yi;LIAO Peiyu;JIA Jianhua;TONG Mingliang(Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education,School of Chemistry,Institute of Green Chemistry and Molecular Engineering,Sun Yat-Sen University,Guangzhou 510006,China)

机构地区：[1]中山大学化学学院,生物无机与合成化学教育部重点实验室,绿色化学与分子工程研究院,广州510006

出　　处：《无机化学学报》2025年第1期141-148,共8页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.22131011,22488101,22071274)资助。

摘　　要：选取了1,1,2,2‑四(4‑吡啶基)乙烯(TEPE)作为桥联配体与Ag(Ⅰ)组装形成阳离子框架,通过引入五氟苯甲酸根(PFB-)或苯甲酸根(Bz-)作为客体得到2例新颖的配合物:[Ag(TEPE)(H_(2)O)](PFB)·7H_(2)O·3EtOH(1)和[Ag(TEPE)](Bz)·4H_(2)O·2EtOH(2)。通过热重分析、红外光谱和单晶X射线衍射等测试对二者的组成与结构进行分析表征。配合物1是一个二维“砖墙”式层状结构,具有经典的hcb拓扑网络。中心Ag(Ⅰ)与分别来自3个TEPE配体的3个氮原子和1个水分子配位,形成四面体的配位几何构型。PFB-客体分布于二维层间,与主体层间产生丰富的超分子相互作用。配合物2则呈现三维网络结构,Ag(Ⅰ)与分别来自4个TEPE配体的4个氮原子配位,Bz-客体填充在c轴方向形成的一维孔道中。配合物2的拓扑结构为sqc8116。在紫外光的激发下,2个配合物均表现出由阴离子客体引起的特征荧光性质。1发射红光,而2则发射蓝光。1,1,2,2‑Tetra(pyridin‑4‑yl)ethene(TEPE)was chosen as a bridging ligand to assemble with Ag(Ⅰ)ions to form the cationic frameworks.And,the pentafluoro‑benzoate anions(PFB-)and the benzoate(Bz-)anions as guests were introduced respectively to generate two new coordination compounds:[Ag(TEPE)(H_(2)O)](PFB)·7H_(2)O·3EtOH(1)and[Ag(TEPE)](Bz)·4H_(2)O·2EtOH(2).The compositions and structures of complexes 1 and 2 were characterized using the thermogravimetric analysis,IR spectra,and single‑crystal X‑ray diffraction analysis.1 possesses a 2D brick‑like coordination layer structure with the classical hcb topology,each Ag(Ⅰ)center is coordinated with an aqua ligand and three N atoms from three TEPE ligands respectively,forming the distorted tetrahedral coordination geometry.The PFB-guests are distributed between the 2D layers to form diverse interactions with the main framework.2 presents a 3D coordination network structure with the sqc8116 topology,in which each Ag(Ⅰ)center is coordinated in a tetrahedral geometry with four N atoms from four TEPE ligands respectively,and Bz-guests are located at the larger channels along the c‑axis.Interestingly,two complexes showed the characteristic fluorescent properties regulated by photoactive guests.Excited by UV light,1 exhibited a red emission while 2 showed a blue emission.CCDC:2389942,1;2389943,2.

关 键 词：1 1 2 2‑四(4‑吡啶基)乙烯 苯甲酸根 金属有机框架 银(Ⅰ) 发光 

分 类 号：O614.122[理学—无机化学]