Highly Selective Bifunctional Luminescent Sensor toward Nitrobenzene and Cu²⁺ Ion Based on Microporous Metal–Organic Frameworks: Synthesis, Structures, and Properties

Abstract

Two metal-organic frameworks (MOFs), namely, [Ni(DTP)(H₂O)]_n (I) and [Cd₂(DTP)₂(bibp)_1.5]_n (II) (H₂DPT = 4'-(4-(3,5-dicarboxylphenoxy) phenyl)-4,2':6',4″-terpyridine; bibp = 1,3-di(1H-imidazol-1-yl)propane), that present structural diversity were solvothermally prepared. Single-crystal X-ray diffraction analysis indicates that they consist of {NiN₂O₄} building units (for I) and {CdO₄N₂} and {CdO₃N₃} building units (for II), which are further linked by multicarboxylate H₂DPT to construct microporous three-dimensional frameworks. The remarkable character of these frameworks is that coordination polymer II demonstrates highly selective and sensitive bifunctional luminescent sensor toward nitrobenzene and Cu²⁺ ion. The fluorescence quenching mechanism of II caused by nitrobenzene is ascribed to electron transfer from electron-rich (II) to electron-deficient nitrobenzene. The result was also evidenced by the density functional theory. Furthermore, anti-ferromagnetic as well as electrochemical characters of Ni-MOF (I) were also investigated in this paper.