Metal–Organic Frameworks Constructed from a New Thiophene-Functionalized Dicarboxylate: Luminescence Sensing and Pesticide Removal

Abstract

A family of thiophene-based metal-organic frameworks (MOFs), [Zn(L)(BBI)·(HO)] (1) (BBI = 1,1'-(1,4-butanediyl)bis(imidazole)) and [Cd(L)(TPOM)]·xS (2) (TPOM = tetrakis(4-pyridyloxy-methylene) methane, S represents noncoordinated solvent molecules) was constructed by employing a new linear thiophene-functionalized dicarboxylic acid (benzo-(1,2;4,5)-bis(thiophene-2'-carboxylic acid, HL) to assemble with d ions in the presence of a flexible ancillary ligand under solvothermal conditions, which exhibit diverse structures. Most strikingly, both compounds 1 and 2 could be efficient luminescent sensory materials that are highly selective and sensitive to environmental contaminants, especially for Hg(II), Cu(II), Cr(VI), and salicylaldehyde, and yet remain unaffected by other molecules that may coexit. Furthermore, this is the first report on MOF-based sensors capable of recyclable detection of Hg(II), Cr(VI), and salicylaldehyde so far. The luminescent sensing mechanism was studied in detail as well. In addition, compound 2 is one of the rare examples of high-performance MOFs trapping 2,4-dichlorophenol from the wasted methanol solution.

Water‐Stable Coordination Polymers as Dual Fluorescent Sensors for Highly Oxidizing Anions Cr2O72− and MnO4−

“…On the other hands, it can be found as well that the emission bands of CP1 – CP3 are strongly overlapped by the absorption bands of MnO 4 − /Cr 2 O 7 2− (Figure S10 c), especially MnO 4 − , suggesting that the resonance energy transfer may take place and lead to the fluorescence quenching. Hence, the combined effect of the competitive absorption and resonance energy transfer could explain the order of quenching constants ( K SV ) and the higher sensitivity of MnO 4 − than Cr 2 O 7 2− , which is also consistent with some previously reported studies . Additionally, the interactions between anions and coordination polymers may also contribute to the quenching effect .…”

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

“…The use of the DBT building block for the design of MOFs has been scarcely explored, being limited to aB DT-dicarboxylic acid to construct luminescent MOFs fort he selective sensing of environmental contaminants. [181] In contrast, BDT building blocksh ave received much more attention for the preparation of COFs, in view of their electronic and optical properties. Bein et al prepared two-dimensional and crystalline mesoporous BDT-COFs (BET = 1946m 2 g À1 )( Figure 18) that were deposited as oriented thin films on indium tin oxide (ITO)-coated glass substrates.…”

Mechanistic Insight into Charge and Energy Transfers of Luminescent Metal–Organic Frameworks Based Sensors for Toxic Chemicals

“…[51][52][53] The increasing demands of society, modern agriculture, pharmaceutical science, and other industrial activities could not have been met without the major contribution of organic solvents, pesticides, and aromatic compounds. [54,55] Furthermore, the extensive use of hazardous substances in chemical and biochemical processes is a major concern in various scientific fields globally, including the health, medical, and environmental industries. [56][57][58][59][60][61] Concentrations of these chemicals in the human body and environment have increased, having various effects.…”