首页 | 本学科首页   官方微博 | 高级检索  
     检索      


Three new ZnII coordination polymers constructed from a semi‐rigid tricarboxylic acid: structural changes caused by flexibility and luminescence sensing for hexavalent chromate anions
Authors:Yanyan An  Liping Lu  Miaoli Zhu
Abstract:Coordination polymers (CPs) with specific structures and functional luminescence have been widely designed as sensors for detecting small molecules and ions. In this study, with or without the help of an N‐donor auxiliary linker, three new ZnII CPs, namely, three‐dimensional (3D) polypentaaquabisμ3‐5‐(4‐carboxybenzyloxy)isophthalato]bisμ6‐5‐(4‐carboxylatobenzyloxy)isophthalato]di‐μ3‐hydroxido‐hexazinc(II)] trihydrate], {Zn6(C16H10O7)2(C16H9O7)2(OH)2(H2O)5]·3H2O}n or {Zn63‐HL)26L)23‐OH)2(H2O)5]·3H2O}n, ( I ), one‐dimensional (1D) catena‐polyaqua(1,10‐phenanthroline)zinc(II)]‐μ2‐5‐(4‐carboxybenzyloxy)isophthalato] dihydrate], {Zn(C16H10O7)(C12H8N2)(H2O)]·2H2O}n or {Zn(μ2‐HL)(phen)(H2O)]·2H2O}n (phen is 1,10‐phenanthroline), ( II ), and 3D polydiaquatetrakis(4,4′‐bipyridine)bisμ6‐5‐(4‐carboxylatobenzyloxy)isophthalato]di‐μ3‐formato‐di‐μ3‐hydroxido‐pentazinc(II)], Zn5(C16H9O7)2(HCOO)2(OH)2(C10H8N2)4(H2O)2]n or Zn54L)2(bpy)42‐OH)23‐HCOO)2(H2O)2]n (bpy is 4,4′‐bipyridine), ( III ), have been constructed from the semi‐rigid tricarboxylic acid 5‐(4‐carboxybenzyloxy)isophthalic acid (H3L) under hydrothermal conditions. CP ( I ) exhibits a twofold interpenetrated 3D+3D→3D skeleton with a 3 , 5 ‐conn topology constructed from triangular trinuclear Zn3(COO)43‐OH)] clusters, in which the H3L ligand adopts three different coordination modes. CP ( II ) exhibits a 1D infinite chain and stacking that gives a 3D structure mediated by hydrogen bonds and weak interactions. CP ( III ) is an interesting 3D 3 , 4 , 8 ‐conn network including linear tetranuclear Zn42‐OH)2(HCOO)2(COO)2] clusters with a new {4·62}2{4·64·8}{46·619·83} topological symbol. The influences of the flexible –CH2–O– linker of the H3L ligand and subtle environmental factors, such as solvent, pH value and auxiliary ligands, on the formation of the final structures are also discussed. The solid‐state fluorescence spectra of CPs ( I )–( III ) were recorded at room temperature and all show better fluorescence performances than H3L. In particular, ( II ) can act as a potential multifunctional fluorescent material for sensing hexavalent chromium ions in aqueous solution with high stability, selectivity and sensitivity. Under ultraviolet light of 365 nm from a UV lamp, a signal response of fluorescence from turning on to off can be observed with the naked eye. It was found that the detection for hexavalent chromium (i.e. Cr2O72?) by ( II ) has a high selectivity KSV = 1.61 × 104M?1 and limit of detection (LOD) = 0.434 µM] in aqueous solution. Quenching mechanisms were also studied in detail.
Keywords:coordination polymer  flexible linker  zinc  tricarboxylic acid  luminescence sensing  crystal structure
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号