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Cheap, stable and easy‐to‐handle Werner ammine salts have been known for more than a century; but they have been rarely used in organic synthesis. Herein, we report that the Werner hexammine complex [Ni(NH3)6]Cl2 can be used as both a nitrogen and a catalytic nickel source that allow for the efficient amination of aryl chlorides in the presence of a catalytic amount of bipyridine ligand under the irradiation of 390–395 nm light without the need of any additional catalysts. More than 80 aryl chlorides, including more than 20 drug molecules, were aminated, demonstrating the practicality and generality of this method in synthetic chemistry. A slow NH3 release mechanism is in operation, obviating the problem of catalyst poisoning. Still interestingly, we show that the Werner salt can be easily recovered and reused, solving the problem of difficult recovery of transition metal nickel catalysts. The protocol thus provides an efficient new strategy for the synthesis of primary aryl amines. [ABSTRACT FROM AUTHOR]

The combination of multiple components or structures into integrated micro/nanostructures for practical application has been pursued for many years. Herein, a series of hierarchical organic microwires with branch, core/shell (C/S), and branch C/S structures are successfully constructed based on organic charge transfer (CT) cocrystals with structural similarity and physicochemical tunability. By regulating the intermolecular CT interaction, single microwires and branch microstructures can be integrated into the C/S and branch C/S structures, respectively. Significantly, the integrated branch C/S microwires, with multicolor waveguide behavior and branch structure multichannel waveguide output characteristics, can function as an optical logic gate with multiple encoding features. This work provides useful insights for creating completely new types of organic microstructures for integrated optoelectronics. [ABSTRACT FROM AUTHOR]

The Buchwald‐Hartwig C‐N coupling reaction has found widespread applications in organic synthesis. Over the past two decades or so, many improved catalysts have been introduced, allowing various amines and aryl electrophiles to be readily used nowadays. However, there lacks a protocol that could be used to couple a wide range of chiral amines and aryl halides, without erosion of the enantiomeric excess (ee). Reported in this article is a method based on molecular Ni catalysis driven by light, which enables stereoretentive C‐N coupling of optically active amines, amino alcohols, and amino acid esters with aryl bromides, with no need for any external photosensitizer. The method is effective for a wide variety of coupling partners, including those bearing functional groups sensitive to bases and nucleophiles, thus providing a viable alternative to accessing synthetically important chiral N‐aryl amines, amino alcohols, and amino acids esters. Its viability is demonstrated by 92 examples with up to 99 % ee. [ABSTRACT FROM AUTHOR]

A highly effective C−O coupling reaction of (hetero)aryl electrophiles with primary and secondary alcohols is reported. Catalyzed by a NiII‐aryl complex under long‐wave UV (390–395 nm) irradiation in the presence of a soluble amine base without any additional photosensitizer, the reaction enables the etherification of aryl bromides and aryl chlorides as well as sulfonates with a wide range of primary and secondary aliphatic alcohols, affording synthetically important ethers. Intramolecular C−O coupling is also possible. The reaction appears to proceed via a NiI–NiIII catalytic cycle. [ABSTRACT FROM AUTHOR]

Using isoreticular chemistry allows the design and construction of a new rare-earth metal (RE) fcu-MOF with a suitable aperture size for practical steric adsorptive separations. The judicious choice of a relatively short organic building block, namely fumarate, to bridge the 12-connected RE hexanuclear clusters has afforded the contraction of the well-defined RE-fcu-MOF triangular window aperture, the sole access to the two interconnected octahedral and tetrahedral cages. The newly constructed RE (Y3+ and Tb3+) fcu-MOF analogues display unprecedented total exclusion of branched paraffins from normal paraffins. The resultant window aperture size of about 4.7 Å, regarded as a sorbate-size cut-off, enabled a complete sieving of branched paraffins from normal paraffins. The results are supported by collective single gas and mixed gas/vapor adsorption and calorimetric studies. [ABSTRACT FROM AUTHOR]

Organic heterostructures (OHs) with multi‐segments exhibit special optoelectronic properties compared with monomeric structures. Nevertheless, the synthesis of multi‐block heterostructures remains challenging due to compatibility issues between segment parts, which restricts their application in optical waveguides and integrated optics. Herein, we demonstrate programmable in‐situ co‐assembly engineering, combining multi‐step spontaneous self‐assembly processes to promote the synthesis of multi‐block heterostructures with a rational arrangement of three or more segments. The rational design of segments enables exciton manipulation and ensures optical waveguides and proper output among the multi‐segment OHs. This work enables the controllable growth of segments within multi‐block OHs, providing a pathway to construct complex OHs for the rational development of future optical applications. [ABSTRACT FROM AUTHOR]