Iron-Catalyzed C-C Bond Cleavage of Oximes for Direct Coupling of Benzothiazole in Water.

An Fe-catalyzed coupling reaction between oxime ester and benzothiazole is described, which involves C-C bond cleavage of oxime ester via a single-electron transfer process. This iron catalytic system performed in water under mild reaction conditions offers a streamlined strategy to the construction of alkyl nitrile substituted benzothiazole derivatives. Application of this strategy for the synthesis of some key important compounds including 4-heterocyclic-3-arylbutanoic acid is also reported.

Electrochemical Oxidative C-H Amination through a Ritter-Type Reaction.

A straightforward strategy for direct benzylic C-H bond amination via an electrochemical Ritter-type reaction is developed. The reaction demonstrates simpler and milder reaction conditions over the existing methods without extra mediator. Moderate to excellent yields up to 94% of the desired amide products were obtained with a broad substrate scope. The removal of the Ac group by a simple step can afford NH-free benzylic amines, providing a suitable approach for the late-stage functionalization of bioactive molecules.

"Point-Line-Plane-Helix" Binuclear Platinum(II) Complexes: Metal-Induced Chirality, Chirality Self-Sorting, and Chiroptical Properties.

Chirality is a fundamental property of nature, and thus, building novel chiral molecules plays a crucial role in multidisciplinary fields. Herein, we have developed a straightforward approach to effectively incorporate all four types of point, axial, planar, and helical chiralities into a single molecule for the first time. The resultant "point-line-plane-helix" binuclear Pt(II) complexes exhibit multiple chiralities, including not only point and axial chiralities from the bridging ligands but also planar and helical chiralities from metal coordination. The intramolecular π-π and Pt-Pt interactions will restrict intramolecular rotations, thereby stabilizing the metal-induced planar and helical chiralities. Furthermore, enantiopure (R,R,R,Rp,M) or (S,S,S,Sp,P) molecules could be obtained by chirality self-sorting without the use of chiral high-performance liquid chromatography. Their single-crystal, circular dichroism, and circularly polarized luminescence properties are comprehensively investigated, providing unequivocal insights into the design of multiple-chirality materials for related applications.

Metal-Induced Planar Chirality of Soft-Bridged Binuclear Platinum(II) Complexes: 100 % Phosphorescence Quantum Yields, Chiral Self-Sorting, and Circularly Polarized Luminescence.

PtII complexes have attracted a great deal of interest due to their rich phosphorescent properties. However, these square-planar PtII complexes are far more likely to encounter the problems of lack of metal-induced chirality and emission "aggregation-caused quenching". Herein, soft-bridged binuclear PtII complexes bearing metal-induced planar chirality were synthesized and characterized. These soft bridging ligands with smaller conjugated system would help to not only improve solubility for synthesis and enantioseparation but also introduce point chirality from amino acid for highly efficient diastereoselectivity. Furthermore, the intramolecular Pt-Pt distances could be well regulated by soft bridging ligands, and consequently the phosphorescence quantum yield up to 100 % could be achieved by shortening intramolecular Pt-Pt distance for first time. These complexes can be used as emitters in highly efficient solution-processed organic light-emitting diodes.

Highly Phosphorescent Planar Chirality by Bridging Two Square-Planar Platinum(II) Complexes: Chirality Induction and Circularly Polarized Luminescence.

Chiral organometallic complexes have demonstrated many potential and practical applications. However, building metal-induced chirality for square-planar complexes still remains a big challenge, because their 2D planar molecular structures are usually superimposable on their mirror images. Herein, we report a straightforward and efficient way to achieve a novel kind of planar chirality by constructing 3D double-layer molecular structures. When the achiral ligand 1,3,4-oxadiazole-2-thiol (OXT) was used to bridge two square-planar complexes, a pair of racemic R/S planar-chiral binuclear Pt(II) complexes was obtained, which could be separated by chiral high-performance liquid chromatography (HPLC). Moreover, enantiopure R,R,R or S,S,S complexes could be prepared by the use of chiral (R)-/(S)-binaphthalene-derived OXT ligands in 99% diastereoselectivity without the use of chiral HPLC. The binaphthalene groups help to ensure good solubility and a smooth amorphous thin film morphology but have little effect on the photophysical properties. The resultant complexes display strong orange-red and near-infrared phosphorescence with quantum yields of up to 83.4% and can be applied as emitters in highly efficient solution-processed organic light-emitting diodes to achieve luminance, luminance efficiency, external quantum efficiency, and an asymmetry factor of up to 3.22 × 104 cd m-2, 28.7 cd A-1, 14.3%, and 2.0 × 10-3, respectively. With a comprehensive consideration of EL efficiency and the asymmetry factor, this is the best performance among Pt(II) complex based circularly polarized OLEDs. Therefore, this work provides a new and simple strategy to build planar chirality for chiroptical and circularly polarized luminescence applications.

Axially Chiral Bis-Cycloplatinated Binaphthalenes and Octahydro-Binaphthalenes for Efficient Circularly Polarized Phosphorescence in Solution-Processed Organic Light-Emitting Diodes.

A new series of axially chiral binuclear Pt(II) complexes with bridging ligands of binaphthalenes and octahydro-binaphthalenes and auxiliary ligands of ß-diketones were designed and prepared. These complexes, identified by spectral and electrochemical methods and single-crystal X-ray diffraction, emit an orange-red phosphorescence with a quantum yield up to 21% and 70% in solution and solid, respectively, due to the effect of steric hindrance from bridging ligands and the 2,3-position extension of chiral axis planes. They can be used as emitters in solution-processed organic light-emitting diodes to achieve luminance efficiency, asymmetry factor, and external quantum efficiency up to 5.4 cd A-1, 3.0 × 10-3, and 3.1%, respectively. Moreover, the essential relationships between their chemical structures and luminescence quantum efficiency and asymmetry factor are discussed, which affords explicit insights for designing circularly polarized luminescent materials and devices.

Transition metal-catalyzed arylation of unstrained C-C single bonds.

Carbon-carbon bond activation is one of the most challenging and important research areas in organic chemistry. Selective C-C bond activation of unstrained substrates is difficult to achieve owing to its inert nature and competitive side reactions, but the ubiquitous presence of C-C bonds in organic molecules makes this transformation attractive and of vital importance. Moreover, transition metal-catalyzed arylation of unstrained C-C single bonds can realize the cleavage of old C-C bonds and introduce important aryl groups into the carbon chain to construct new C-C bonds at the same time, providing a powerful and straightforward method to reconstruct the skeleton of the molecules. In recent years, considerable progress has been made in the area of direct arylation of C-C bonds, and ß-C elimination or oxidative addition strategies play key roles in these transformations. This review summarizes recent achievements of transition metal-catalyzed arylation of unstrained C-C bonds, demonstrated by various kinds of substrates including alcohol, nitrile and carbonyl compounds, and each example is detailed by its corresponding mechanism, catalytic system and scope of the substrate.

Iron(III)-Catalyzed Highly Regioselective Halogenation of 8-Amidoquinolines in Water.

A simple protocol of iron(III)-catalyzed halogenation of 8-amidoquinolines in water under mild conditions was developed, affording the 5-halogenlated products in good to excellent yields up to 98%. The reaction mechanism most likely involves a single-electron transfer (SET) process.

Unusual Circularly Polarized and Aggregation-Induced Near-Infrared Phosphorescence of Helical Platinum(II) Complexes with Tetradentate Salen Ligands.

A series of chiral and helical PtII -Salen complexes with 1,1'-binaphthyl linkers were synthesized and characterized. Owing to the restriction of intramolecular motions of central 1,1'-binaphthyls, the complexes exhibit unusual near-infrared aggregation-induced phosphorescence (AIP). The (R)/(S) enantiopure complexes were characterized by X-ray diffraction, circular dichroism spectra, time-dependent density functional theory calculations, and circularly polarized luminescence (CPL). The present work explores the use of tetradentate ligands that can be easily prepared from commercially available enantiopure compounds, and the subsequent preparation of stable CPL-active square planar PtII complexes with AIP effect that may have interest in many applications.

Synthesis of benzimidazoles by CuI-catalyzed three-component reaction of 2-haloaniline, ammonia and aldehyde in water.

An efficient copper-catalyzed three-component reaction of 2-haloaniline, ammonia and aldehyde for the synthesis of benzimidazoles with 1,10-phenanthroline as the ligand has been developed. A variety of substituted benzimidazole derivatives can be obtained in yields up to 95%.

A Class of Multiresponsive Colorimetric and Fluorescent pH Probes via Three Different Reaction Mechanisms of Salen Complexes: A Selective and Accurate pH Measurement.

We report a class of multiresponsive colorimetric and fluorescent pH probes based on three different reaction mechanisms including cation exchange, protonation, and hydrolysis reaction of K(I), Ca(II), Zn(II), Cu(II), Al(III), and Pd(II) Salen complexes. Compared with traditional pure organic pH probes, these complex-based pH probes exhibited a much better selectivity due to the shielding function of the filled-in metal ion in the complex. Their pH sensing performances were affected by the ligand structure and the central metal ion. This work is the first report of "off-on-on'-off" colorimetric and fluorescent pH probes that possess three different reaction mechanisms and should inspire the design of multiple-responsive probes for important analytes in biological systems.

Fluorescent metal ion chemosensors via cation exchange reactions of complexes, quantum dots, and metal-organic frameworks.

Due to their wide range of applications and biological significance, fluorescent sensors have been an active research area in the past few years. In the present review, recent research developments on fluorescent chemosensors that detect metal ions via cation exchange reactions (transmetalation, metal displacement, or metal exchange reactions) of complexes, quantum dots, and metal-organic frameworks are described. These complex-based chemosensors might have a much better selectivity than the corresponding free ligands/receptors because of the shielding function of the filled-in metal ions. Moreover, not only the chemical structure of the ligands/receptors but also the identity of the central metal ions have a tremendous impact on the sensing performances. Therefore, sensing via cation exchange reactions potentially provides a new, simple, and powerful way to design fluorescent chemosensors.

Correction: Fluorescent metal ion chemosensors via cation exchange reactions of complexes, quantum dots, and metal-organic frameworks.

Correction for 'Fluorescent metal ion chemosensors via cation exchange reactions of complexes, quantum dots, and metal-organic frameworks' by Jinghui Cheng, et al., Analyst, 2015, DOI: 10.1039/c5an01398d.

Palladium-catalyzed direct arylation of phenols with aryl iodides.

An efficient protocol of palladium-catalyzed direct para-arylation of unfunctionalized phenols with aryl iodides under mild conditions was reported. A variety of substrates were applied in this reaction with yields up to 87%.

Synthesis of dibenzothiophenes by Pd-catalyzed dual C-H activation from diaryl sulfides.

Palladium-catalyzed dual C-H functionalization of diaryl sulfides to form dibenzothiophenes (DBTs) by oxidative dehydrogenative cyclization is reported. This protocol afforded various DBTs in moderate to good yields with tolerance of a wide variety of substrates. Benzo[1,2-b:4,5-b']bis[b]benzothiophene was successfully synthesized by this method, which was used as an organic semiconductor for field-effect transistors.

Optical chemosensors based on transmetalation of salen-based Schiff base complexes.

We report our systematic studies of novel, simple, selective, and sensitive optical (both colorimetric and fluorescent) chemosensors for detecting Al(3+) based on transmetalation reactions (metal displacement or exchange reactions) of a series of K(I), Ca(II), Zn(II), Cu(II), and Pt(II) complexes containing different ligands of salen-based Schiff bases. Both the chemical structure of the salen ligand and the identity of the central metal ion have a tremendous impact on the sensing performance, which is mainly determined by the stability constant of the complex. Moreover, the selectivities of the salen-complex-based chemosensors are much better than those of the corresponding free salen ligands because of the shielding function of the filled-in metal ion in the complex. Therefore, the present work potentially provides a new and simple way to design optical probes via complex-based transmetalation reactions.

Near-infrared phosphorescence: materials and applications.

Room-temperature phosphorescent materials that emit light in the visible (red, green, and blue; from 400 to 700 nm) have been a major focus of research and development during the past decades, due to their applications in organic light-emitting diodes (OLEDs), light-emitting electrochemical cells, photovoltaic cells, chemical sensors, and bio-imaging. In recent years, near-infrared (NIR) phosphorescence beyond the visible region (700-2500 nm) has emerged as a new, promising, and challenging research field with potential applications toward NIR OLEDs, telecommunications, night vision-readable displays. Moreover, NIR phosphorescence holds promise for in vivo imaging, because cells and tissues exhibit little absorption and auto-fluorescence in this spectral region. This review describes the overall progress made in the past ten years on NIR phosphorescent transition-metal complexes including Cu(I), Cu(II), Cr(III), Re(I), Re(III), Ru(II), Os(II), Ir(III), Pt(II), Pd(II), Au(I), and Au(III) complexes, with a primary focus on material design complemented with a selection of optical, electronic, sensory, and biologic applications. A critical comparison of various NIR phosphorescent materials reported in the literature and a blueprint for future development in this field are also provided.

Copper-catalyzed formation of N,N-dimethyl benzamide from nitrile and DMF under an O2 atmosphere.

Amidation of nitrile with N,N-dimethylformamide (DMF) was catalyzed by Cu2O with 1,10-phenanthroline as a ligand under an oxygen atmosphere. A variety of N,N-dimethyl benzamides were obtained in yields up to 84%.

Synthesis of disulfides and diselenides by copper-catalyzed coupling reactions in water.

A simple and efficient protocol for copper-catalyzed coupling reactions between aryl halides and elemental sulfur or selenium has been developed. A variety of disulfides and diselenides can be obtained in moderate to excellent yields up to 96%.

Cu-catalyzed three-component synthesis of substituted benzothiazoles in water.

Three in one: Copper-catalyzed three-component reactions, involving 2-iodoanilines, aldehydes, and sulfur powder, afford 2-phenylbenzothiazoles in water. A variety of 2-substituted benzothiazoles can be obtained in good to excellent yields of up to 96 % (see scheme).