Spin-Distribution-Directed Regioselective Substitution Strategy for Highly Stable Olympicenyl Radicals

The synthesis of bench-stable conjugated π-radicals is challenging owing to the lack of modular approaches, which greatly hampers their practical material screens and applications. Here, we demonstrate a spin-distribution-directed regioselective substitution strategy to introduce substituents into the specific positions of an olympicenyl radical in a stepwise manner, resulting in a series of highly stable radical species. The substituents can also adjust the crystal packing by means of steric and electronic factors, enabling the changing from a π-dimer to a pseudo-one-dimensional chain. The first single crystal organic field-effect transistor device based on a graphenic radical is fabricated in air, showing a hole mobility of up to 0.021 cm² V⁻¹ s⁻¹ and excellent device stability. This approach may be generalized to diverse spin-delocalized open-shell organic radicals.     

Type-II Red Phosphorus: Wavy Packing of Twisted Pentagonal Tubes

Elemental phosphorus exhibits fascinating structural varieties and versatile properties. The unique nature of phosphorus bonds can lead to the formation of extremely complex structures, and detailed structural information on some phosphorus polymorphs is yet to be investigated. In this study, we investigated an unidentified crystalline phase of phosphorus, type-II red phosphorus (RP), by combining state-of-the-art structural characterization techniques. Electron diffraction tomography, atomic-resolution scanning transmission electron microscopy (STEM), powder X-ray diffraction, and Raman spectroscopy were concurrently used to elucidate the hidden structural motifs and their packing in type-II RP. Electron diffraction tomography, performed using individual crystalline nanowires, was used to identify a triclinic unit cell with volume of 5330 ų, which is the largest unit cell for elemental phosphorus crystals up to now and contains approximately 250 phosphorus atoms. Atomic-resolution STEM imaging, which was performed along different crystal-zone axes, confirmed that the twisted wavy tubular motif is the basic building block of type-II RP. Our study discovered and presented a new variation of building blocks in phosphorus, and it provides insights to clarify the complexities observed in phosphorus as well as other relevant systems.     

In-situ experiment tests and particulate simulations on powder paving process of additive manufacturing

In this work, in-situ experimental tests are first performed to investigate the powder spreading process of additive manufacturing, where different kinds of scrapers and spreading speeds are employed. Detailed kinetic behaviours of individual powder particles are discussed by discrete element method simulations. It is found that the decrease of inclination angle of the scraper improves the powder pressure and compaction in the spreading process, leading to a denser powder flow and thus a denser powder bed. The increase of spreading speed also improves the powder pressure and compaction in the spreading process. However, the powder flow becomes looser due to the volume dilation, and thus the quality of the paved powder bed decreases. In industrial applications, if the higher powder spreading speed is employed to improve the processing efficiency, the scraper with a smaller inclination angle can be used to ensure the powder bed quality.