An olympicenyl radical, a spin 1/2 hydrocarbon radical with C 2v symmetry and uneven spin distribution, remains elusive despite the considerable theoretical research interest. Herein, we report syntheses of two air-stable olympicenyl radical derivatives, OR1 and OR2, with half-life times (τ1/2) in air-saturated solution of 7 days and 34 days. The high stability was ascribed to kinetic blocking of reactive sites with high spin densities. X-ray crystallographic analysis revealed unique 20-center–2-electron head-to-tail π-dimer structures with intermolecular distances shorter than the sum of van der Waals radius of carbon. The ground state of the π-dimers was found to be singlet, with singlet–triplet energy gaps estimated to be −2.34 kcal/mol and −3.28 kcal/mol for OR1 and OR2, respectively, by variable-temperature electron spin resonance (ESR) spectroscopy. The monomeric radical species were in equilibrium with the π-dimer in solution, and the optical and electrochemical properties of the monomers and π-dimers in solution were investigated by UV–vis–NIR spectroscopy and cyclic voltammetry, revealing a concentration-dependent nature. Theoretical calculations illustrated that upon formation of a π-dimer the local aromaticity of each monomer was enhanced, and spatial ring current between the monomers was present, which resulted in an increment of aromaticity of the interior of the π-dimer.

Large-area uniform of single-crystal tungsten disulfide (WS) is important for advanced optoelectronics based on two-dimensional (2D) atomic crystals. However, difficulties in controlling the interrelated growth parameters restrict its development in devices. Herein, we present the synthesis of triangular monolayered WS flakes with good uniformity and single crystal by adjusting the introduction time of sulfur precursor and the distances between the sources and substrates to control the nucleation density. Investigation of the morphology and structure by transmission electron microscopy and Raman spectroscopy indicates that a series of triangular (side length of 233 μm) monolayered WS flakes shows high-quality structure and homogenous crystallinity. Field-effect transistors based on the fabricated triangular monolayered WS with single crystal demonstrate environmentally stable charge transport with a field-effect mobility of 50.5 cm/V s and current modulation I/ I of ∼10. The results of this study pave the way for the application of monolayered WS in a multitude of 2D-material-based devices.

In this work, both negative and positive magnetoresistance (MR) in solution-processed regioregular poly(3-hexylthiophene) (RR-P3HT) is observed in organic spin valves (OSVs) with vertical LaSrMnO (LSMO)/P3HT/AlO/Co configuration. The ferromagnetic (FM) LSMO electrode with near-atomic flatness is fabricated by a DC facing-target magnetron sputtering method. This research is focused on the origin of the MR inversion. Two types of devices are investigated in details: One with Co penetration shows a negative MR of 0.2%, while the other well-defined device with a nonlinear behavior has a positive MR of 15.6%. The MR measurements in LSMO/AlO/Co and LSMO/Co junctions are carried to exclude the interference of insulating layer and two FM electrodes themselves. By examining the Co thicknesses and their corresponding magnetic hysteresis loops, a spin-dependent hybrid-interface-state model by Co penetration is induced to explain the MR sign inversion. These results proven by density functional theory (DFT) calculations may shed light on the controllable interfacial properties in designing novel OSV devices.

Organic spintronic devices present one of the most appealing technologies for future spintronic devices by taking advantage of the spin degree of freedom. Conjugated polymers are attractive for the exemplified device of organic spin valves (OSVs) due to their weak spin–orbit coupling, solution-processability, low production cost, and mechanical flexibility. However, the performance of polymer SVs is a matter of debate, as the evaporated top ferromagnetic (FM) electrode will penetrate into the organic layer during a typical fabrication process, especially in the device with an organic layer thickness of nanometers. It will cause a severe problem in controllable and reproducible spin manipulations, not to mention the clarification of the spin-dependent transport mechanism. Here, a universal, simple, and low-cost method based on a transferred electrode is developed for a polymer spin valve with stable and reliable state operation. It is demonstrated in an OSV device with a vertical structure of La2/3Sr1/3MnO3 (LSMO)/P3HT/AlO x /Co/Au that this approach not only builds a damage-free interface between magnetic electrodes and an organic spacer layer but also can be generalized for other devices with delicate active layers. Furthermore, a multistate writing and reading prototype is achieved on the premise of robust and quick magnetic response. The results reveal the importance of a spinterface and effective thickness of the organic layer in fundamental spintronic research and may lead to a strong potential in future flexible, large-area, and robust organic multifunctional circuits.

No abstract

No abstract

We report a novel solid-state molecular device structure based on double self-assembled monolayers (D-SAM) incorporated into the suspended nanowire architecture to form a “Au|SAM-1||SAM-2|Au” junction. Using commercially available thiol molecules that are devoid of synthetic difficulty, we constructed a “Au|S-(CH2)6-ferrocene||SAM-2|Au” junction with various lengths and chemical structures of SAM-2 to tune the coupling between the ferrocene conductive molecular orbital and electrode of the junction. Combining low noise and a wide temperature range measurement, we demonstrated systematically modulated conduction depending on the length and chemical nature of SAM-2. Meanwhile, the transport mechanism transition from tunneling to hopping and the intermediate state accompanied by the current fluctuation due to the coexistence of the hopping and tunneling transport channels were observed. Considering the versatility of this solid-state D-SAM in modulating the electrode–molecule interface and electroactive groups, this strategy thus provides a novel facile strategy for tailorable nanoscale charge transport studies and functional molecular devices.

Plant growth in semi-arid ecosystems is usually severely limited by soil nutrient availability. Alleviation of these resource stresses by fertiliser application and aboveground litter input may affect plant internal nutrient cycling in such regions. We conducted a 4-year field experiment to investigate the effects of nitrogen (N) addition (10 g N·m(-2) ·year(-1)) and plant litter manipulation on nutrient resorption of Leymus chinensis, the dominant native grass in a semi-arid grassland in northern China. Although N addition had no clear effects on N and phosphorus (P) resorption efficiencies in leaves and culms, N fertilisation generally decreased leaf N resorption proficiency by 54%, culm N resorption proficiency by 65%. Moreover, N fertilisation increased leaf P resorption proficiency by 13%, culm P resorption proficiency by 20%. Under ambient or enriched N conditions, litter addition reduced N and P resorption proficiencies in both leaves and culms. The response of P resorption proficiency to litter manipulation was more sensitive than N resorption proficiency: P resorption proficiency in leaves and culms decreased strongly with increasing litter amount under both ambient and enriched N conditions. In contrast, N resorption proficiency was not significantly affected by litter addition, except for leaf N resorption proficiency under ambient N conditions. Furthermore, although litter addition caused a general decrease of leaf and culm nutrient resorption efficiencies under both ambient and enriched N conditions, litter addition effects on nutrient resorption efficiency were much weaker than the effects of litter addition on nutrient resorption proficiency. Taken together, our results show that leaf and non-leaf organs of L. chinensis respond consistently to altered soil N availability. Our study confirms the strong effects of N addition on plant nutrient resorption processes and the potential role of aboveground litter, the most important natural fertiliser in terrestrial ecosystems, in influencing plant internal nutrient cycling.