Yanyu Qi

Moving Beyond Boron-Based Substituents To Achieve Phosphorescence in Tellurophenes

Previous research in our group showed that tellurophenes with pinacolboronate (BPin) units at the 2- and/or 5-positions displayed efficient phosphorescence in the solid state, both in the presence of oxygen and water. In this current study, we show that luminescence from a tellurophene is possible when various aryl-based substituents are present, thus greatly expanding the family of known (and potentially accessible) Te-based phosphors. Moreover, for the green phosphorescent perborylated tellurium heterocycle, 2,3,4,5-TeC4BPin4 (4BTe), oxygen-mediated quenching of phosphorescence is an important contributor to the lack of emission in solution (when exposed to air); thus, this system displays aggregation-enhanced emission (AEE). These discoveries should facilitate the future design of color tunable tellurium-based luminogens.

Constitutional Dynamic Chemistry-based New Concept of Molecular Beacons for High Efficient Development of Fluorescent Probes

Inspired by the concept of constitutional dynamic chemistry, we propose a new and well-adaptable strategy for developing molecular beacon (MB)-like fluorescent probes. To demonstrate the strategy, we synthesized and used an amino group containing pyrenyl derivative of cholesterol (CP) for the construction of new fluorescent probes with EDTA and sulfuric acid. The probes as created were successfully used for n-hexane purity checking and Ba(2+)and Pb(2+)sensing, respectively.

Reunderstanding the Fluorescent Behavior of Four-Coordinate Monoboron Complexes Containing Monoanionic Bidentate Ligands

We demonstrated for the first time that, at temperatures below the melting point of a given polar solvent, the emission of some four-coordinate monoboron complexes containing monoanionic bidentate (NO) ligands shifted to lower wavelengths, but no such shift was observed for studies conducted in nonpolar solvents. This means that the emission from a polar solvent appears at shorter wavelengths if compared with that from a nonpolar solvent when the measurement was performed at low temperatures, a phenomenon totally different from that observed for conventional solvatochromic fluorophores. The finding was rationalized by considering the temperature-dependent conformational relaxation of the tetrahedron monoboron complexes from their local excited (LE) state to their relaxed excited (RE) state. Further studies revealed that variating the structure of the chelating ligands could result in remarkable changes in the fluorescent colors of the monoboron complexes. However, changing the structure of other two monodentate ligands showed little effect upon the fluorescence property of the compounds. Therefore, it is anticipated that the monoboron complexes may be taken as a platform to construct a variety of functional molecular systems via alternating the structure of the chelating ligand and that of the monodentate ligand. As an example, naphthalene was introduced as a monodentate ligand, and independent emissions from naphthalene unit and the other part of the monoboron complex as well as intramolecular energy transfer between them were observed. It is believed that the present work provides a new insight into the monoboron complexes, laying the foundation for them to be explored for developing novel molecular systems.

Dynamic Chemistry-Based Sensing: A Molecular System for Detection of Saccharide, Formaldehyde, and the Silver Ion

Development of artificial complex molecular systems is of great importance in understanding complexity in natural processes and for achieving new functionalities. One of the strategies is to create them via optimized utilization of noncovalent interactions and dynamic covalent bonds. We report here on a new complex molecular system, which was constructed by integrating the multiple interactions containing a dynamic covalent interaction between 1,2-diol and boronic acid, a coordination interaction between the silver ion and pyridyl, and an easy accessible reaction between secondary amine and formaldehyde. By employing the three dynamic interactions, a pyrene (Py) labeled fluorophore, PPB, was designed and synthesized. The compound reacts with fructose (F), a monosaccharide, in aqueous phase and produces a fluorescent adduct, PPB-F, which can be further used as a sensing platform for formaldehyde (FA) and the silver ion. The respective dynamic interactions are accompanied with color changes due to the reversible switching between Py-monomer emission and excimer emission. The respective experimental detection limits (DLs) for the three analytes are much lower than 0.2 mM, 0.1 mM, and 2.5 μM, respectively. The presence of relevant compounds or ions shows little effect upon the sensing. No doubt, the results as presented show that the integration of supramolecular interactions including dynamic covalent bonds can be employed as a general strategy to develop new functional molecular systems or materials.

Non-contact identification and differentiation of illicit drugs using fluorescent films

Sensitive and rapid identification of illicit drugs in a non-contact mode remains a challenge for years. Here we report three film-based fluorescent sensors showing unprecedented sensitivity, selectivity, and response speed to the existence of six widely abused illicit drugs, including methamphetamine (MAPA), ecstasy, magu, caffeine, phenobarbital (PB), and ketamine in vapor phase. Importantly, for these drugs, the sensing can be successfully performed after 5.0 × 105, 4.0 × 105, 2.0 × 105, 1.0 × 105, 4.0 × 104, and 2.0 × 102 times dilution of their saturated vapor with air at room temperature, respectively. Also, presence of odorous substances (toiletries, fruits, dirty clothes, etc.), water, and amido-bond-containing organic compounds (typical organic amines, legal drugs, and different amino acids) shows little effect upon the sensing. More importantly, discrimination and identification of them can be realized by using the sensors in an array way. Based upon the discoveries, a conceptual, two-sensor based detector is developed, and non-contact detection of the drugs is realized.Sensitive and rapid identification of illicit drugs in a non-contact mode remains a challenge. Here, the authors report three film-based fluorescent sensors showing remarkable sensitivity, selectivity and response speed to six widely abused illicit drugs in vapor phase.

Highly Sensitive and Discriminative Detection of BTEX in the Vapor Phase: A Film-Based Fluorescent Approach

BTEX (benzene, toluene, ethylbenzene, o-xylene, m-xylene, and p-xylene) represents a group of volatile organic compounds (VOCs) and constitutes a great threat to human health. However, sensitive, selective, and speedy detection of them on-site and in the vapor phase remains a challenge for years. Herein, we report a film-based fluorescent approach and a conceptual sensor, which shows unprecedented sensitivity, speed, and reversibility to the aromatic hydrocarbons in the vapor phase. In the studies, pentiptycene was employed to produce a nonplanar perylene bisimide (PBI) derivative, P-PBI. The compound was further utilized to fabricate the film. The novelty of the design is the combination of capillary condensation and solvent effect, which is expected to enrich the analytes from vapor phase and shows outputs at the same time. Importantly, the film permits instant response (∼3 s) and real-time identification (<1 min) of benzene and toluene from other aromatic hydrocarbons. The experimental detection limits (DLs) of the six analytes are lower than 9.2, 2.7, 1.9, 0.2, 0.4, and 0.4 ppm, which with the exception of benzene, are significantly lower than the NIOSH recommended long-term exposure limits. More importantly, the film is photochemically stable, and more than 300 repetitive tests showed no observable bleaching. In addition, the sensing is fully reversible. The superior performance of the film device is in support of the assumption that the combination of capillary condensation and solvation effect would constitute an effective way to design high-performance fluorescent films, especially for challenging chemical inert and photoelectronically inactive VOCs.