One-pot synthesis of double silane-functionalized carbon dots with tunable emission and excellent coating properties for WLEDs application

Silane-functionalized carbon dots (SiCDs) can be exploited as effective color converting materials for the solid-state light-emitting devices. However, most of SiCDs reported thus far have shown photoluminescence emissions in the blue and green spectral range, which limit them to construct an efficient white light-emitting diodes (WLEDs) due to the lack of long-wavelength emission. Herein, a series of double silane-functionalized carbon dots (DSiCDs) were prepared via a one-step solvothermal method. The results show that the organic functional group of the silane has great influence on the optical properties of DSiCDs and the number of alkoxy group in the silane has great influence on coating properties of DSiCDs. In addition, the DSiCDs prepared by (3-aminopropyl)triethoxysilane and N-[3-(Trimethoxysilyl)propyl]ethylenediamine with molar ratio of 7:3 show excellent optical properties with the maximum emission at 608 nm under 400 nm excitation. Furthermore, they can be completely dried within 1 h at room temperature to form fluorescent coating with high stability and strong adhesion to the substrate. Together with their excellent optical and coating properties, they can be directly coated on LED chips to prepare WLEDs, with a CIE coordinate of (0.33,0.31), color rendering index of 81.6, and color temperature of 5774 K.

Polar Alkoxy Group and Pyridyl Effects on the Mesomorphic Behavior of New Non-Symmetrical Schiff Base Liquid Crystals

A series of non-symmetrical Schiff base liquid crystals were prepared and investigated. Schiff bases of p-alkyloxy aniline derivatives and 4-phenyl pyridine-4′-carbaldehyde were synthesized. The terminal alkoxy groups substituting aniline are of varied chain length, namely C6, C8, and C16. The structures of the compounds were confirmed via 1H NMR and 13C NMR spectroscopy. Different mesophases of the samples were thermally and optically characterized by differential thermal analysis (DSC) and polarized optical microscopy (POM). All samples revealed enantiotropic smectic B (SmB) and smectic A (SmA) mesophases. The results obtained were further correlated with the density functional theory (DFT) theoretical calculations. The results are compared to a series of compounds bearing biphenyl moiety in their mesogens. The thermal stabilities of the different mesophase reduced upon the increment of the alkoxy chain length. The temperature ranges of both the smectic mesophases of new compounds bearing the 4-phenyl pyridine moiety are generally expanded higher than the other series. In addition, the total mesophase range is greater in the new compounds when compared to their biphenyl analogues. The DFT results were investigated in terms of the molecular geometries and the frontier molecular orbitals as well as the charge distribution mapping to show and illustrate the difference in the mesomorphic properties.

Axial-Ligand-Cleavable Silicon Phthalocyanines Triggered by Near-Infrared Light toward Design of Photosensitizers for Photoimmunotherapy

Near-infrared photoimmunotherapy (NIR-PIT) is a novel phototherapy for the treatment of cancer that uses NIR light and conjugates of antibody-IR700, a silicon phthalocyanine photosensitizer. A key feature of NIR-PIT is light-induced axial ligand cleavage of IR700, which finally causes cytotoxicity. Here, we focused on protonation of the axial ligand on the IR700 anion radical during the photochemical process. The Gibbs energy in the protonation reaction of IR700 derivatives with different axial ligands was calculated. These calculations suggested the order of the cleavage efficiency corresponds to the basicity of the axial ligand (i.e. alkoxy > siloxy (IR700) > phenoxy ≈ oxycarbonyl), which was confirmed by the photoirradiation experiments with synthesized compounds. Thus, axial ligand cleavage is significantly dependent on the basicity of the axial ligand. Our findings suggest that PIT reagent with an IR700 derivative bearing alkoxy group would show better efficacy than IR700.

Selective Esterification of Phosphonic Acids

Here, we report straightforward and selective synthetic procedures for mono- and diesterification of phosphonic acids. A series of alkoxy group donors were studied and triethyl orthoacetate was found to be the best reagent as well as a solvent for the performed transformations. An important temperature effect on the reaction course was discovered. Depending on the reaction temperature, mono- or diethyl esters of phosphonic acid were obtained exclusively with decent yields. The substrate scope of the proposed methodology was verified on aromatic as well as aliphatic phosphonic acids. The designed method can be successfully applied for small- and large-scale experiments without significant loss of selectivity or reaction yield. Several devoted experiments were performed to give insight into the reaction mechanism. At 30 °C, monoesters are formed via an intermediate (1,1-diethoxyethyl ester of phosphonic acid). At higher temperatures, similar intermediate forms give diesters or stable and detectable pyrophosphonates which were also consumed to give diesters. 31P NMR spectroscopy was used to assign the structure of pyrophosphonate as well as to monitor the reaction course. No need for additional reagents and good accessibility and straightforward purification are the important aspects of the developed protocols.

Development of Chiral N-Alkoxyamide Strategy and Application to Asymmetric Total Synthesis of Fasicularin

The asymmetric total synthesis of fasicularin by a chiral N-alkoxyamide strategy is reported. Incorporation of the chiral alkoxy group to an amide nitrogen changes the original reactivity of the amide, enabling two key transformations: aza-spirocyclization and the reductive Strecker reaction. In the aza-spirocyclization, DFT calculations indicate that pyramidalization of the alkoxyamide nitrogen is crucial to control the reactivity. The chiral alkoxy group is also used as a stereocontrol element to establish two consecutive stereocenters. The iridium-catalyzed reductive Strecker reaction of the N-alkoxylactam provides the aminonitrile with high diastereoselectivity.

Development of calix[4]arenes modified at their narrow- and wider-rims as potential metal ions sensor layers for microcantilever sensors: further studies

The development of a microcantilever (MCL) sensing device capable of simultaneously detecting several metal ionic species in aqueous media with low limits of detection requires a variety of sensing layers which are ion-specific. Calix[4]arenes are robust molecules which can be easily modified and have been extensively studied for their ion binding properties. They are also capable of forming self-assembled monolayers (SAMs) onto the gold layers of MCLs and are capable of detecting various metal ions with different anionic counterions in aqueous solutions. In this paper we report on the effect of the alkoxy group in the narrow rim [O-(alkoxycarbonyl)methoxy] substituents of bimodal calix[4]arenes which have been used as metal ion MCL sensing layers, using classical solution state experimental studies. A DFT computational study to compare the experimental results with several metal ions is also reported herein.

One-step direct oxidation of fullerene-fused alkoxy ethers to ketones for evaporable fullerene derivatives

Ketones are widely applied moieties in designing functional materials and are commonly obtained by oxidation of alcohols. However, when alcohols are protected/functionalized, the direct oxidation strategies are substantially curbed. Here we show a highly efficient copper bromide promoted one-step direct oxidation of benzylic ethers to ketones with the aid of a fullerene pendant. Mechanistic studies unveil that fullerene can serve as an electron pool proceeding the one-step oxidation of alkoxy group to ketone. In the absence of the fullerene pendant, the unreachable activation energy threshold hampers the direct oxidation of the alkoxy group. In the presence of the fullerene pendant, generated fullerene radical cation can activate the neighbour C–H bond of the alkoxy moiety, allowing a favourable energy barrier for initiating the direct oxidation. The produced fullerene-fused ketone possesses high thermal stability, affording the pin-hole free and amorphous electron-transport layer with a high electron-transport mobility.

New Nitro-Laterally Substituted Azomethine Derivatives; Synthesis, Mesomorphic and Computational Characterizations

Two new homologues series, based on two rings of the azomethine central group bearing the terminal alkoxy group of various chain lengths, were prepared. The alkoxy chain length varied between 6 and 16 carbons. The other terminal wing in the first series was the F atom, and the compound is named N-4-florobenzylidene-4-(alkoxy)benzenamine (In). The second group of compounds included a lateral NO2 substituent in addition to the terminal F atom, named N-(4-fluoro-3-nitrobenzylidene)-4-(alkyloxy)aniline (IIn). Mesomorphic and optical properties were carried out via differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Elemental analyses, FT-IR, and NMR spectroscopy were carried out to elucidate the molecular structures of the synthesized groups. Mesomorphic investigations indicated that all the synthesized homologues (In) were monomorphic, possessing the smectic A (SmA) phase monotropically, while the second group (IIn) members were non-mesomorphic. The experimental data indicated that the formation of the mesophase is affected by the protrusion of the lateral nitro group. The disruption of the mesophase in the second group was attributed to the increase of its molecular width, which affects its lateral intermolecular interactions. The computational simulations were in agreement with the experimental data. On the other hand, the location of NO2 group within the molecular geometry increased the melting temperature of the molecule, and thus, affected their thermal and physical properties. By discussing the estimated parameters, it was found that the molecular architecture, the dipole moment, and the polarizability of the investigated compounds are highly affected by the electronic nature and position of the terminal and lateral substituents as well as their volumes.

One-Step Direct Oxidation of Alkoxy to Ketone for Evaporable Fullerene-Fused Ketone as Efficient Electron-Transport Materials

Ketones, one of widely applied moieties in designing electrical and medical materials, commonly converted from the alcohols through the oxidation reactions. However, when alcohols are protected/functionalized, the direct oxidation strategies are substantially curbed. Here we show a highly efficient copper bromide promoted one-step direct oxidation of alkoxy to ketone with the aid of a fullerene pendant. Mechanistic studies unveil that fullerene can serve as an electron poor proceeding the one-step oxidation of alkoxy group to ketone. In the absence of fullerene pendant, the unreachable activation energy threshold hampers the direct oxidation of alkoxy group. In the presence of fullerene pendant, copper bromide oxidized fullerene radical cation can activate neighboring C–H bond of alkoxy moieties, allowing a favorable energy barrier for initiating the direct oxidation of alkoxy group. Produced fullerene-fused ketone indicates high thermal stability, affording the pin-hole free and amorphous electron-transport layer with high electron-transport mobility.

Covalent modification of Black phosphorus with alkoxy group to improve the solubility and ambient stability

Black phosphorus (BP), a new 2D material as a layered allotrope of phosphorus, has regained attention due to its outstanding semiconductor characteristics. However, the major hurdle of using few-layer BP...