K2CO3/18-Crown-6-Catalyzed Selective H/D Exchange of Heteroarenes with Bromide as a Removable Directing Group.

The K2CO3/18-crown-6-catalyzed H/D exchange of heretoarenes in high atom % deuterium incorporation is disclosed. The use of a weak base as a catalyst leads to excellent site selectivity and broad functional group tolerance. Control experiments indicated that the use of bromide, which enhances the adjacent C-H bond reactivity, as a removable directing group is essential. Moreover, conversion of bromide to other functional groups is also performed to construct other useful deuterated compounds.

Carbon-polymer dot-based UV absorption and fluorescence performances for heavy metal ion detection.

In previous reports, carbon dots (CDs) were customarily used as fluorescent probes to detect heavy metal ions. However, scientists neglected to take advantage of the excellent UV absorption properties of CDs to detect heavy metal ions. Herein, we synthesized nitrogen-containing carbon polymer dots (N-CPDs) for the determination of Co2+ ions in water samples by a one-step hydrothermal method using l-histidine and ethylene imine polymer as raw materials. The N-CPDs were characterized by ultraviolet-visible spectrum (UV-vis), infrared spectrum (FT-IR), X-ray photoelectron spectrum (XPS) and transmission electron microscopy (TEM) techniques. They possess superior full-band UV absorption performance and the surface is rich in multifunctional groups such as -COOH, -CN-, -OH, etc. When Co2+ was added to N-CPDs solution, the color of the solution rapidly changed from colorless to yellow-brown, which was visible to the naked eye. The UV absorption intensity of N-CPDs changed, and the fluorescence was instantly quenched, due to the formation of chelate between Co2+ and N-CPDs, and the FRET process occurred. The detection of Co2+ showed good linearity for both fluorescence and UV absorption spectroscopy modes in the range of 0-200 µM, and the limit of detection were 1.0023 µM and 0.75 µM, respectively. These two methods have the advantages of simple operation, remarkable selectivity and small sample size, which can be applied to the field detection of Co2+ in water samples. It is possible to develop the UV absorption properties of CDs to detect the ions.

Silver salt enabled H/D exchange at the ß-position of thiophene rings: synthesis of fully deuterated thiophene derivatives.

We disclose a silver catalyzed H/D exchange reaction, which can introduce the deuterium atom at the ß position of thiophene rings without the assistance of any coordinating groups. The advantages of this reaction include operation in open air, usage of D2O as the deuterium source, good tolerance to a range of functional groups and obtaining high atom% deuterium incorporation. In addition, this H/D exchange reaction is employed for direct deuteration of a thiophene based monomer, which is usually prepared by multistep synthesis from expensive deuterated starting materials.

Construction of Carbon Dots with Color-Tunable Aggregation-Induced Emission by Nitrogen-Induced Intramolecular Charge Transfer.

As one of the most promising fluorescent nanomaterials, the fluorescence of carbon dots (CDs) in solution is extensively studied. Nevertheless, the synthesis of multicolor solid-state fluorescence (SSF) CDs is rarely reported. Herein, CDs with multicolor aggregation-induced emission are prepared using amine molecules, all of them exhibiting dual fluorescence emission at 480 nm (Em-1) and 580-620 nm (Em-2), which is related to the SS bonds of dithiosalicylic acid and the conjugated structure attached to CO/CN bonds, respectively. As a strong electron-withdrawing group, the increase of CN content makes dual-fluorescent groups on the surface of CDs produce push and pull electrons, which determines intramolecular charge transfer (ICT) between the double emission. With the increase in CN content from 35.6% to 58.4%, the ICT efficiency increases from 8.71% to 45.94%, changing the fluorescence of CDs from green to red. The increase of ICT efficiency causes fluorescence quantum yield enhancement by nearly five times and redshift of the fluorescence peak. Finally, based on the multicolor luminescence properties induced by the aggregation of CDs, pattern encryption and white-LED devices are realized. Based on the fat solubility and strong ultraviolet absorption characteristics of CDs, fingerprint detection and leaf anti-UV hazards are applied.

C-H Bond Functionalization of (Hetero)aryl Bromide Enabled Synthesis of Brominated Biaryl Compounds.

Aryl bromide is one of the most important compounds in organic chemistry, because it is widely used as synthetic building blocks enabling quick access to a wide array of bioactive molecules, organic materials, and polymers via the versatile cutting-edge transformations of C-Br bond. Direct C-H bond functionalization of aryl bromide is considered to be an efficient way to prepare functionalized aryl bromides; however, it is rarely explored possibly due to the relatively low reactivity of aryl bromide toward C-H bond activation. We herein report a palladium-catalyzed coupling reaction between aryl iodide and aryl bromide for preparing brominated biaryl compounds via a silver-mediated C-H bond activation pathway.

Red, orange, yellow and green luminescence by carbon dots: hydrogen-bond-induced solvation effects.

The mechanism of the solvation-dependent multicolor luminescence of carbon dots (CDs) is not clear, despite the fact that multicolor luminescent CDs have important applications in many fields. In this article, we report solvated chromogenic CDs with productivity of up to 57%. The luminescence of the CD particles exhibits a regular redshift in N,N-dimethylformamide (DMF), ethanol, water, and acetic acid. The redshift of the CDs may be ascribed to the linking of the CD surfaces to the solvent through hydrogen bonds (HB). Different surface level states are formed by HB between the surfaces of the CDs and the solvent, and differences in dispersion states lead to different energy resonance transfer (ETR) efficiencies. The CDs/B2O3 composite exhibits excellent fluorescence thermal stability, and it has also been used to manufacture white-light-emitting devices with a high color rendering index of 87. Additionally, the excellent solvation effects of the CDs have application prospects in the detection of the water content in organic solvents. Finally, the CDs are used to realize cell imaging and positioning, which has significant application prospects in biological fields.

Synthesis of Multideuterated (Hetero)aryl Bromides by Ag(I)-Catalyzed H/D Exchange.

Deterium-labeled (hetero)aryl bromide is one of the most widespread applicable motifs to achieve important deuterated architectures for various scientific applications. Traditionally, these deterium-labeled (hetero)aryl bromides are commonly prepared via multistep syntheses. Herein, we disclose a direct H/D exchange protocol for deuteration of (hetero)aryl bromides using Ag2CO3 as catalyst and D2O as deuterium source. This protocol is highly efficient, simply manipulated, and appliable for deuterium-labeling of over 55 (hetero)aryl bromides including bioactive druglike molecules and key intermediates of functional materials. In addition, this method showed distinguishing site-selectivity toward the existing transition-metal-catalyzed HIE process, leading to multideuterated (hetero)aryl bromides in one step.

Ultralong lifetime and efficient room temperature phosphorescent carbon dots through multi-confinement structure design.

Room temperature phosphorescence materials have inspired extensive attention owing to their great potential in optical applications. However, it is hard to achieve a room temperature phosphorescence material with simultaneous long lifetime and high phosphorescence quantum efficiency. Herein, multi-confined carbon dots were designed and fabricated, enabling room temperature phosphorescence material with simultaneous ultralong lifetime, high phosphorescence quantum efficiency, and excellent stability. The multi-confinement by a highly rigid network, stable covalent bonding, and 3D spatial restriction efficiently rigidified the triplet excited states of carbon dots from non-radiative deactivation. The as-designed multi-confined carbon dots exhibit ultralong lifetime of 5.72 s, phosphorescence quantum efficiency of 26.36%, and exceptional stability against strong oxidants, acids and bases, as well as polar solvents. This work provides design principles and a universal strategy to construct metal-free room temperature phosphorescence materials with ultralong lifetime, high phosphorescence quantum efficiency, and high stability for promising applications, especially under harsh conditions.

Ag(i)-Mediated hydrogen isotope exchange of mono-fluorinated (hetero)arenes.

An efficient approach to install deuterium into mono-fluorinated (hetero)arenes by a Ag2CO3/Sphos-mediated HIE protocol with D2O as the deuterium source has been disclosed. This method showed a specific site selectivity of deuteration at the α-position of the fluorine atom, which is complementary to the existing transition metal-catalyzed HIE process.

Room temperature phosphorescence from Si-doped-CD-based composite materials with long lifetimes and high stability.

C-dot-based composites with phosphorescence have been widely reported due to their attractive potential in various applications. But easy quenching of phosphorescence induced by oxygen or instability of matrices remained a tricky problem. Herein, we reported a Si-doped-CD (Si-CD)-based RTP materials with long lifetime by embedding Si-CDs in sulfate crystalline matrices. The resultant Si-CD@sulfate composites exhibited a long lifetime up to 1.07 s, and outstanding stability under various ambient conditions. The intriguing RTP phenomenon was attributed to the C = O bond and the doping of Si element due to the fact that sulfates could effectively stabilize the triplet states of Si-CDs, thus enabling the intersystem crossing (ISC). Meanwhile, we confirmed that the ISC process and phosphorescence emission could be effectively regulated based on the heavy atom effect. This research introduced a new perspective to develop materials with regulated RTP performance and high stability.

Self-formed C-dot-based 2D polysiloxane with high photoluminescence quantum yield and stability.

C-Dots and composites based on them face the challenges of poor stability, especially under photo-radiation, and low solid-state photoluminescence quantum yields (PLQYs), which hinder their application in optical devices. Herein, a novel 2-dimensional hybrid material of polysiloxane embedded with Si-doped carbon dots (P-E-Si-CDs) was synthesized by a self-assembly approach, and the hybrid composite exhibited broadband blue-green fluorescence emission, outstanding photostability, high thermal stability, and a high PLQY of 82.8%. Moreover, the dual fluorescent emissions were demonstrated the creation of two closed-loop fluorophores. Using the as-prepared hybrid fluorescent material, fabricated light-emitting diodes (LEDs) based on UV and blue-emitting LED chips present safe warm white light emission and adjustable white emission with a high color rendering index of up to 91, respectively. This work provides a novel strategy for the design and realization of Si-CD-based hybrid composites, thus promising their prospective use commercially in LED lighting.

Enhancement of Fluorescence Emission for Tricolor Quantum Dots Assembled in Polysiloxane toward Solar Spectrum-Simulated White Light-Emitting Devices.

Commercial white light-emitting diodes (LEDs) have the undesirable characteristics of blue-rich emission and low color rendering index (CRI), while the constituent quantum dots (QDs) suffer from aggregation-induced fluorescence quenching and poor stability. Herein, a strategy is developed to assemble tricolor QDs into a polysiloxane matrix using a polymer-mediated hybrid approach whereby the hybrid composite exhibits a significant enhancement of aggregation-dispersed emission, outstanding photostability, high thermal stability, and outstanding fluorescence recovery. Using the as-prepared hybrid fluorescent materials, the fabricated LEDs exhibit solar spectrum-simulated emission with adjustable Commission Internationale de L'Eclairage coordinates, correlated color temperature, and a recorded CRI of 97. Furthermore, they present no ultraviolet emission and weak blue emission, thus indicating an ideal healthy and high-CRI white LED lighting source.

Correction: Cascade alkylation and deuteration with aryl iodides via Pd/norbornene catalysis: an efficient method for the synthesis of congested deuterium-labeled arenes.

Correction for 'Cascade alkylation and deuteration with aryl iodides via Pd/norbornene catalysis: an efficient method for the synthesis of congested deuterium-labeled arenes' by Lei Guo et al., Chem. Commun., 2019, 55, 8567-8570.

Ag2CO3-Catalyzed H/D Exchange of Five-Membered Heteroarenes at Ambient Temperature.

Ag2CO3-catalyzed hydrogen isotope exchange of five-membered heteroarenes is disclosed. The reaction can be conducted in the open air, at ambient temperature, and with D2O as deuterium source. Moreover, this protocol showed orthogonal site selectivity to existing technology, thereby greatly expanding the scope of substrates for HIE reaction. The mechanistic study indicated that the carbonate group plays a crucial role to achieve high levels of deuterium incorporation by lowering the activation energy of H/D exchange process.

Cascade alkylation and deuteration with aryl iodides via Pd/norbornene catalysis: an efficient method for the synthesis of congested deuterium-labeled arenes.

An efficient approach for synthesizing congested deuterium-labeled arenes via cascade alkylation and deuteration with aryl iodides has been disclosed. We found that the adoption of sodium formate-d as a deuterium source is the key for achieving high deuterium incorporation >98%.

Synthesis of modified carbon dots with performance of ultraviolet absorption used in sunscreen.

The research and development of non-toxic, broad-spectrum and environmentally friendly ultraviolet absorbers remains no significant progress in recent years. We found that the ultraviolet absorption spectra can be regulated through modification of functional groups on carbon dots surface, and the modified carbon dots exhibiting good stability and functions of sunscreen (Sun protection actor reaches to 22) and anti-aging properties were experimentally demonstrated. Moreover, we figured out the ultraviolet absorption mechanism of carbon dots for the first time and confirmed the existence of non-fluorescent radiation energy traps. Carbon dots are expected to be widely used and commercialized as ultraviolet absorbers.

Synthesis of Silicon Quantum Dots with Highly Efficient Full-Band UV Absorption and Their Applications in Antiyellowing and Resistance of Photodegradation.

UV absorbers are very effective in the fields of antiyellowing, resistance of photocatalytic degradation, and sunscreen cosmetics. However, commercialized UV absorbers have the drawbacks of toxicity, low absorption efficiency, transparency, etc. Here, we report for the first time silicon quantum dots as full-band UV absorbers. The NH-refunctionalized silicon quantum dots with high-performance UV absorption were successfully synthesized under the synergistic effect of sodium citrate and ethanediamine, and the (NH, OH)-functionalized silicon quantum dots (SiQDs) with full-band UV absorption can be achieved by reregulating -NH2 and -OH groups on the surface. The as-prepared (NH, OH)-functionalized SiQDs exhibited good stability and underwent treatment of varying pH and temperature. Furthermore, experimental results demonstrated that compared to commercial water-soluble organic UV absorbers, the (NH, OH)-functionalized SiQDs showed better antiyellowing performance for polyurethane and resistance of photocatalytic degradation for rhodamine B, and presented huge application potential in sunscreen cosmetics. Finally, the UV absorption mechanism of SiQDs was explained to be mainly related to Γ â†’ Γ direct band gap transition, which absorb UV light and release it as thermal radiation.

Assembly of shell/core CDs@CaF2 nanocomposites to endow polymers with multifunctional properties.

The shell/core structure of CDs@CaF2 nanocomposites (CCNCs) were prepared by assembling fluorescent carbon dots (CDs) inside the inorganic CaF2 substrates using co-precipitation interaction. CDs endow CaF2 with properties of good UV-absorbing behavior and efficient blue light emission instead of rare-earth such as Eu that is expensive and susceptible to polluting the environment during the mining process. Due to the nanometer size and surface effect of nano CaF2, and the approximate refractive index between CaF2 and polyethylene (PE), CCNC/PE film exhibits better elongation at the break than pure PE film while maintaining high transparency and visible light transmittance. Simultaneously, the CCNC/PE film was experimentally demonstrated to have outstanding performance of anti-UV and blue light conversion, which shows that CCNCs can be a novel and promising multifunctional additive applied in polymers especially for greenhouse film.