ABSTRACT
BACKGROUND: Nitroaromatic compounds are inherently hazardous and explosive, so convenient and rapid detection strategies are needed for the sake of human health and the environment. There is an urgent demand for chemical sensing materials that offer high sensitivity, operational simplicity, and recognizability to effectively monitor nitroaromatic residues in industrial wastewater. Despite its importance, the mechanisms underlying fluorescence quenching or enhancement in fluorescent sensing materials have not been extensively researched. The design and synthesis of multiresponsive fluorescent sensing materials have been a great challenge until now. RESULTS: In this study, a one-dimensional Cd-based fluorescent porous coordination polymer (Cd-CIP-1) was synthesized using 5-(4-cyanobenzyl)isophthalic acid (5-H2CIP) and 4,4'-bis(1-imidazolyl)biphenyl (4,4'-bimp) and used for the selective detection of nitrobenzene in aqueous solution by fluorescence quenching, with a limit of detection of 1.38 × 10-8 mol L-1. The presence of aniline in the Cd-CIP-1 solution leads to the enhancement of fluorescence property. Density functional theory and time-dependent density functional theory calculations were carried out to elucidate the mechanisms of the fluorescence changes. This study revealed that the specific pore size of Cd-CIP-1 facilitates analyte screening and enhances host-guest electron coupling. Furthermore, π-π interactions and hydrogen bond between Cd-CIP-1 and the analytes result in intermolecular orbital overlap and thereby boosting electron transfer efficiency. The different electron flow directions in NB@Cd-CIP-1 and ANI@Cd-CIP-1 lead to fluorescence quenching and enhancement. SIGNIFICANCE AND NOVELTY: The multiresponsive coordination polymer (Cd-CIP-1) can selectively detect nitrobenzene and recognize aniline in aqueous solutions. The mechanism of fluorescence quenching and enhancement has been thoroughly elucidated through a combination of density functional theory and experimental approaches. This study presents a promising strategy for the practical implementation of a multiresponsive fluorescent chemical sensor.
ABSTRACT
The improper utilization of nitrobenzene (NB) and ornidazole (ORN) has resulted in irreversible effects on the environment. By combining experimental investigation, density functional theory (DFT) calculations, and machine learning, an effective green strategy for detecting NB and ORN in aqueous solutions can be developed. In this study, a one-dimensional Cd-based coordination polymer (Cd-HCIA-3) was designed and synthesized using 5-((4-carboxybenzyl)oxy)isophthalic acid and rigid 2,2'-bipyridine under solvothermal reaction conditions. Cd-HCIA-3 exhibits excellent fluorescence properties and stability in aqueous solutions. DFT calculations were performed to predict the fluorescence sensing performance of Cd-HCIA-3, revealing that photoinduced electron transfer is the key mechanism for inducing fluorescence quenching in the presence of NB and ORN, with weak molecular interactions promoting electron transfer. Fluorescence sensing experiments were conducted to verify the DFT results, showing that Cd-HCIA-3 can selectively detect NB and ORN in aqueous solutions with limits of detection of 7.22 × 10-8 and 1.31 × 10-7 mol/L, respectively. This study's findings provide valuable insights into the design and synthesis of fluorescent coordination polymers for target analytes.
ABSTRACT
Transition-metal coordination complexes have attracted wide attention in molecular chemistry, but their applications still confront a tremendous challenge. Herein, a novel silver coordination polymer with a formula of {[Ag9(TIPA)6](NO3)9·12H2O}n (Ag-TIPA) was prepared by a solvothermal reaction of silver nitrate with triangular tris(4-imidazolylphenyl)amine (TIPA). The crystalline molecular structure was determined by single-crystal X-ray diffraction, which showed that each Ag(I) was coordinated with two nitrogen atoms of TIPA ligands. Such Ag-TIPA was used as a catalyst for the photodegradation of ciprofloxacin and 4-nitrophenol under UV-visible light irradiation. The results exhibited excellent photocatalytic performance and reusability due to high structure stability in an acidic, neutral and alkaline environment. The experimental findings and density functional theory calculations revealed that metal-ligand charge transfer in Ag-TIPA extended the absorption range of light and improved the charge transfer properties of TIPA. To further understand the photodegradation process, the intermediates were predicted and analysed through electrostatic potential, orbital weighted dual descriptor, and liquid chromatography-mass spectrometry techniques. Based on these findings, a possible degradation mechanism was proposed. This study provides new insights into the design and synthesis of Ag-based coordination polymers with novel structures, excellent catalytic activity, and good durability.
ABSTRACT
Nitroaromatic compounds in aqueous undermine environmental sustainability and affect human health. The development of a fluorescent sensor capable of efficiently and selectively detecting trace amounts of nitroaromatic compounds presents a considerable challenge. This study introduced Zn/Cd isomeric coordination polymers (Zn-H2CIA-1/Cd-H2CIA-2), which are synthesized using 5-((4-carboxybenzyl)oxy)isophthalic acid (5-H3CIA) and 1,10-phenanthroline (Phen). The polymers have zero-dimensional discrete crystal structure with a six-coordinated scissor-like shape. The two coordination polymers can be used as fluorescent sensors for detecting nitrobenzene (NB) and demonstrated favorable sensitivity, with detection limits of 1.95 × 10-8 and 4.66 × 10-7 mol/L, respectively. Zn-H2CIA-1 exhibited stronger fluorescence and a more sensitive response to NB compared with Cd-H2CIA-2. To elucidate their fluorescence-quenching mechanisms, we analyzed Zn-H2CIA-1 by performing DFT and TD-DFT calculations. The pore structure, density of states, excitation energy, hole-electron distribution, and orbital composition were analyzed. The suitable size of pores in Zn-H2CIA-1 is the main reason for its high NB selectivity. Moreover, intermolecular π-π stacking interactions result in an orbital overlap between Zn-H2CIA-1 and NB, enabling the transfer of electrons from Zn-H2CIA-1 to NB. This electron transfer is identified as the fundamental cause of fluorescence quenching in Zn-H2CIA-1.
ABSTRACT
Water environment pollution is becoming an increasingly serious issue due to industrial pollutants with the rapid development of modern industry. Among many pollutants, the toxic and explosive nitroaromatics are used extensively in the chemical industry, resulting in environmental pollution of soil and groundwater. Therefore, the detection of nitroaromatics is of great significance to environmental monitoring, citizen life and homeland security. Lanthanide-organic complexes with controllable structural features and excellent optical performance have been rationally designed and successfully prepared and used as lanthanide-based sensors for the detection of nitroaromatics. This review will focus on crystalline luminescent lanthanide-organic sensing materials with different dimensional structures, including the 0D discrete structure, 1D and 2D coordination polymers and the 3D framework. Large numbers of studies have shown that several nitroaromatics could be detected by crystalline lanthanide-organic-complex-based sensors, for instance, nitrobenzene (NB), nitrophenol (4-NP or 2-NP), trinitrophenol (TNP) and so on. The various fluorescence detection mechanisms were summarized and sorted out in the review, which might help researchers or readers to comprehensively understand the mechanism of the fluorescence detection of nitroaromatics and provide a theoretical basis for the rational design of new crystalline lanthanide-organic complex-based sensors.
