Reversible and Stepwise Single-Crystal-to-Single-Crystal Transformation of a Platinum(II) Complex with Vapochromic Luminescence

The vapochromic single-crystal-to-single-crystal (SCSC) transformation of a highly luminescent Pt^II complex bearing an N-heterocyclic carbene [Pt(CN)₂(tBu-impy)] (tBu-impyH⁺=1-tert-butyl-3-(2-pyridyl)-1H-imidazolium) is reported. The trihydrate form of the complex, which exhibits blue ³MMLCT emission owing to weak Pt⋅⋅⋅Pt interactions, changed its luminescence color from blue to yellowish-green upon the desorption of water molecules while keeping the high emission quantum yield of more than 0.45. Variable-temperature and continuous in-situ tracking of single-crystal X-ray diffraction measurements revealed that the SCSC transformation proceeds reversibly by the release and reabsorption of water molecules, thereby changing the stacked structure slightly. As a result, the dynamics of vapor-induced SCSC transformation were elucidated: that the anhydrous form returned to the original trihydrate form in a two-step process under a water vapor atmosphere. In addition, the Pt^II complex exhibited a similar SCSC response accompanied by a luminescence color change in the presence of methanol vapor, while being inactive toward ethanol vapor.     

Synthesis and crystal structures of novel glycoluril carboxylic acids conglomerates

The two novel conglomerates were obtained by crystallization of racemic (2'S,3aS,6aR)/(2'R,3aR,6aS) (glycoluril-1-yl)-3-methylbutanoic acid and (2'R,3aR,6aR)/(2'S,3aS,6aS) (4,6-dimethylglycoluril-1-yl)pentanoic acid synthesized by highly diastereoselective condensation of 4,5-dihydroxy- imidazolidin-2-ones with racemic ureido acids. The differences in the molecular geometry of synthesized racemates were studied by X-ray diffraction that showed them to crystallize as conglomerates in non-centrosymmetric space groups Pna2₁ and P2₁2₁2₁, respectively     

Assessing the Importance of Cation Size in the Tetragonal-Cubic Phase Transition in Lithium-Garnet Electrolytes**

Lithium garnets are promising solid-state electrolytes for next-generation lithium-ion batteries. These materials have high ionic conductivity, a wide electrochemical window and stability with Li metal. However, lithium garnets have a maximum limit of seven lithium atoms per formula unit (e.g., La₃Zr₂Li₇O₁₂), before the system transitions from a cubic to a tetragonal phase with poor ionic mobility. This arises from full occupation of the Li sites. Hence, the most conductive lithium garnets have Li between 6–6.55 Li per formula unit, which maintains the cubic symmetry and the disordered Li sub-lattice. The tetragonal phase, however, forms the highly conducting cubic phase at higher temperatures, thought to arise from increased cell volume and entropic stabilisation permitting Li disorder. However, little work has been undertaken in understanding the controlling factors of this phase transition, which could enable enhanced dopant strategies to maintain room temperature cubic garnet at higher Li contents. Here, a series of nine tetragonal garnets were synthesised and analysed by variable temperature XRD to understand the dependence of site substitution on the phase transition temperature. Interestingly the octahedral site cation radius was identified as the key parameter for the transition temperature with larger or smaller dopants altering the transition temperature noticeably. A site substitution was, however, found to make little difference irrespective of significant changes to cell volume.     

Graphdiyne-actinyl complexes as potential catalytic materials: A DFT perspective from their structural,bonding, electronic and redox properties

Versatile graphdiyne (GDY) substrate has been modified by numerous transition metals and resulting composites showed excellent photo/electro-catalytic performance. However, GDY materials modified by actinides that are stockpiled waste product due to large-scale use in nuclear industry, are particularly scarce and remains great challenge. To deeply understand the structural properties, GDY complexating actinyl (An^mO₂)ⁿ⁺ (An = U, Np, Pu; m = VI, V) species with its atomistic pore was investigated by relativistic density functional theory (DFT). The GDY pore was found suitable to hold actinyl species, by forming organometallic AnC dative bonds. This chemical coupling interaction was further confirmed by quantum theory of atoms-in-molecule and electronic structure calculations. The GDY-uranyl(V), for instance, shows a π(UC) bonding HOMO, which is anticipated to improve electron transfer between ligand and metal. Orbital structures and compositions of complexes suggest their implication towards catalysis, which were further corroborated by calculations on redox potentials of GDY-actinyl complexes. Hence, our results show the potential applications of GDY complexating actinyl species towards novel catalytic surfaces.     

Effects of lanthanides doping on the optical properties of graphene/WSe2 heterostructure based on ab-initio calculations

Based on the density functional theory, we discussed the electronic and optical properties of graphene/ WSe₂ (GW) heterostructure after lanthanides doping. Red shift appears and the optical parameter values are improved in the low energy region after the lanthanides are doped. Different doping types are also discussed. In the case of single doping, substitute Yb atom on W site will improve the peak values of the optical parameters greatly. In the case of co-doping, it is found that the effect will be more obvious when the two doped lanthanide atoms are located in the second neighboring positons. These results suggest that lanthanides doping does adjust the electronic structure and improve the optical properties of GW heterostructures, which providing useful guidance for the design of novel optical nanodevices based on two-dimensional materials.     

基于石墨烯/石墨烯卷轴复合薄膜高灵敏度柔性压力传感器

一维导电材料例如纳米线，大量应用于柔性压力传感器中. 但是一维材料和基底之间接触时相互作用力较弱，使得传感器灵敏度、响应时间、和循环寿命等性能指标有待进一步提高. 针对这些问题，设计了石墨烯/石墨烯卷轴多分子层复合薄膜作为传感器导电层. 石墨烯卷轴具有一维结构，而石墨烯的二维结构可以牢固地固定卷轴，以确保高导电性复合薄膜与基底之间的粘附性，同时整体结构的导电通道得到了增加. 由于一维和二维结构的协同效应，实现了应变灵敏度系数3.5 kPa^-1、 响应时间小于50 ms、能够稳定工作1000次以上的压阻传感器.     

Prediction of resolvent mode shapes in supersonic turbulent boundary layers

This work applies resolvent analysis to compressible zero-pressure-gradient turbulent boundary layers with freestream Mach numbers between 2 and 4, focusing exclusively on large scale motions in the outer region of the boundary layer. We investigate the effects of Mach number on predicted flow structures, and in particular, look at how such effects may be attributed to changes in mean properties. By leveraging the similarity between the compressible and incompressible resolvent operators, we show that the shape of the streamwise velocity and temperature components of resolvent response modes in the compressible regime can be approximated by applying ideas from wavepacket pseudospectral theory to a simple scalar operator. This gives a means of predicting the shape of resolvent mode components for compressible flows without requiring the singular value decompositions of discretized operators. At a Mach number of 2, we find that accurate results are obtained from this approximation when using the compressible mean velocity profile. At Mach numbers of 3 and 4, the quantitative accuracy of these predictions is improved by also considering a local effective Reynolds number based on the local mean density and viscosity.     

Electrical switching effect in a photochromic molecule between two graphene electrodes

We propose a single-molecule electrical switches consisting of a photochromic dimethyldihydropyrene/cyclophanediene molecule sandwiched between two graphene electrodes and investigate the electronic transport by using density-functional theory and nonequilibrium Green's function methods. The “open” and “closed” isomers of the photochromic molecule are shown to have electrical switching behavior and negative differential resistance effect. Moreover, it is also found that the switching ratio between two different conductive states depends on the ambient temperature, and the device behaves as a stable electrical switch around room temperature, which is in agreement with a recent experimental study of another photochromic molecule diarylethene reported by Jia et al. (2016) [17].