Pseudo-mono-axial ligand fields that support high energy barriers in triangular dodecahedral Dy(iii) single-ion magnets

The synthesis of air-stable, high-performance single-molecule magnets (SMMs) is of great significance for their practical applications. Indeed, Ln complexes with high coordination numbers are satisfactorily air stable. However, such geometries easily produce spherical ligand fields that minimize magnetic anisotropy. Herein, we report the preparation of three air-stable eight-coordinate mononuclear Dy(iii) complexes with triangular dodecahedral geometries, namely, [Dy(BPA-TPA)Cl](BPh₄)₂ (1) and [Dy(BPA-TPA)(X)](BPh₄)₂·nCH₂Cl₂ (X = CH₃O⁻ and n = 1 for 2; L = PhO⁻ and n = 2 for 3), using a novel design concept in which the bulky heptadentate [2,6-bis[bis(2-pyridylmethyl)amino]methyl]-pyridine (BPA-TPA) ligand enwraps the Dy(iii) ion through weak coordinate bonds leaving only a small vacancy for a negatively charged (Cl⁻), methoxy (CH₃O⁻) or phenoxy (PhO⁻) moiety to occupy. Magnetic measurements reveal that the single-molecule magnet (SMM) property of complex 1 is actually poor, as there is almost no energy barrier. However, complexes 2 and 3 exhibit fascinating SMM behavior with high energy barriers (U_eff = 686 K for 2; 469 K for 3) and magnetic hysteresis temperatures up to 8 K, which is attributed to the pseudolinear ligand field generated by one strong, highly electrostatic Dy–O bond. Ab initio calculations were used to show the apparent difference in the magnetic dynamics of the three complexes, confirming that the pseudo-mono-axial ligand field has an important effect on high-performance SMMs compared with the local symmetry. This study not only presents the highest energy barrier for a triangular dodecahedral SMM but also highlights the enormous potential of the pseudolinear Dy–L ligand field for constructing promising SMMs.

Air-stable triangular dodecahedral Dy(iii) single-ion magnets with pseudo-mono-axial linear ligand fields exhibit high energy barrier exceeding 600 K, which represent the highest energy barrier for mononuclear SMMs with triangular dodecahedron.     

Thiazole fused S,N-heteroacene step-ladder polymeric semiconductors for organic transistors

Ladder-type thiazole-fused S,N-heteroacenes with an extended π-conjugation consisting of six (SN6-Tz) and nine (SN9-Tz) fused aromatic rings have been synthesized and fully characterized. To date, the synthesis of well-defined fused building blocks and polymers of π-conjugated organic compounds based on the thiazole moiety is a considerable synthetic challenge, due to the difficulty in their synthesis. Acceptor–donor building blocks M1 and M2 were successfully polymerized into ladder homopolymers P1–P2 and further copolymerized with a diketopyrrolopyrrole unit to afford step-ladder copolymer P3. The optical, electronic, and thermal properties, in addition to their charge transport behavior in organic thin-film transistors (OTFTs), were investigated. The results showed an interesting effect on the molecular arrangement of the thiazole-based ladder-type heteroacene in the crystal structure revealing skewed π–π-stacking, and expected to possess better p-type semiconducting performance. The polymers all possess good molecular weights and excellent thermal properties. All the polymer-based OTFT devices exhibit annealing temperature dependent performance, and among the polymers P3 exhibits the highest mobility of 0.05 cm² V⁻¹ s⁻¹.

Ladder-type thiazole-fused S,N-heteroacenes with an extended π-conjugation consisting of six (SN6-Tz) and nine (SN9-Tz) fused aromatic rings have been synthesized and fully characterized.     

Backbone-controlled LUMO energy induces intramolecular C–H activation in ortho-bis-9-borafluorene-substituted phenyl and o-carboranyl compounds leading to novel 9,10-diboraanthracene derivatives

The choice of backbone linker for two ortho-bis-(9-borafluorene)s has a great influence on the LUMO located at the boron centers and, therefore, the reactivity of the respective compounds. Herein, we report the room temperature rearrangement of 1,2-bis-(9-borafluorenyl)-ortho-carborane, C₂B₁₀H₁₀-1,2-[B(C₁₂H₈)]₂ ([2a]) featuring o-carborane as the inorganic three-dimensional backbone and the synthesis of 1,2-bis-(9-borafluorenyl)benzene, C₆H₄-1,2-[B(C₁₂H₈)]₂ (2b), its phenylene analog. DFT calculations on the transition state for the rearrangement support an intramolecular C–H bond activation process via an S_EAr-like mechanism in [2a], and predicted that the same rearrangement would take place in 2b, but at elevated temperatures, which indeed proved to be the case. The rearrangement gives access to 3a and 3b as dibora-benzo[a]fluoroanthene isomers, a form of diboron polycyclic aromatic hydrocarbon (PAH) that had yet to be explored. The isolated compounds 2b, 3a, and 3b were fully characterized by NMR, HRMS, cyclic voltammetry (CV), single-crystal X-ray diffraction analysis, and photophysical measurements, supported by DFT and TD-DFT calculations.

The backbone linker for two ortho-bis-(9-borafluorene)s influences the LUMO at the boron centers and the reactivity of the respective compounds.     

A Novel （4,6）-Connected Net Based on Dysprosium Benzenedicarboxylate, [Dy（OAc）（BDC）]n

A new lanthanide coordination polymer, [Dy（OAc）（BDC）]n 1 （OAc = acetate, BDC = 1,4-benzenediacarboxylate）, has been synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analysis reveals that complex 1 has infinite zigzag Dy-OAc chains, which are further connected by BDC to form a 3D metal-organic framework. According to topology analysis, this framework can be characterized as （4,6）-connected （3.4.54）（32.4.56.66） net that has never been reported before. Crystal structure for 1： space group Pbca, a = 13.314（3）, b = 8.0269（18）, c = 20.275（5）A, V= 2166.8（9）A3, C10H7O6Dy, Mr = 385.66, Z= 8, Dc = 2.364 g/cm^3, μ= 6.910 mm^-1, F（000） = 1448, the final R = 0.0181 and wR = 0.0520.     

An Improved Temporal Fusion Transformers Model for Predicting Supply Air Temperature in High-Speed Railway Carriages

A key element for reducing energy consumption and improving thermal comfort on high-speed rail is controlling air-conditioning temperature. Accurate prediction of air supply temperature is aimed at improving control effects. Existing studies of supply air temperature prediction models are interdisciplinary, involving heat transfer science and computer science, where the problem is defined as time-series prediction. However, the model is widely accepted as a complex model that is nonlinear and dynamic. That makes it difficult for existing statistical and deep learning methods, e.g., autoregressive integrated moving average model (ARIMA), convolutional neural network (CNN), and long short-term memory network (LSTM), to fully capture the interaction between these variables and provide accurate prediction results. Recent studies have shown the potential of the Transformer to increase the prediction capacity. This paper offers an improved temporal fusion transformers (TFT) prediction model for supply air temperature in high-speed train carriages to tackle these challenges, with two improvements: (i) Double-convolutional residual encoder structure based on dilated causal convolution; (ii) Spatio-temporal double-gated structure based on Gated Linear Units. Moreover, this study designs a loss function suitable for general long sequence time-series forecast tasks for temperature forecasting. Empirical simulations using a high-speed rail air-conditioning operation dataset at a specific location in China show that the temperature prediction of the two units using the improved TFT model improves the MAPE by 21.70% and 11.73%, respectively the original model. Furthermore, experiments demonstrate that the model effectively outperforms seven popular methods on time series computing tasks, and the attention of the prediction problem in the time dimension is analyzed.     

代际流动性的地区差异及影响因素—来自中国的微观证据

代际流动性是测度社会不平等的重要指标,区域发展不平衡则是中国的客观现实。运用人口普查数据和中国城市年鉴,可发现中国现阶段代际流动性的三个特征：（1）全国层面的代际收入弹性为0.673。（2）代际流动性呈现出显著的地区及城市差异,沿海、北方的代际流动性明显高于内陆及南方。代际收入弹性最低的省会城市是天津（0.107）,最高的是江西南昌（0.686）;地级市分别是山东莱芜（0.124）和云南丽江（0.76）。（3）具有以下特征的地区具有更高的代际流动性：沿海及经济发达地区,高校更多、中小学教育投入更多的地区,非少数民族聚集地,革命老区。从微观机理上分析代际流动性的地区差异,可以为中国区域平衡发展政策提供理论依据。     

在高压氧下豚鼠听觉诱发电位的变化

豚鼠暴露在两个绝对压下呼吸高压氧,比较了暴露前后短声诱发的听神经动作电位(AP)、脑干电位(BSEP)及听皮层电位(ACEP)的潜伏期和振幅。主要结果是:在呼吸高压氧期间AP和BSEP的振幅明显增高,但ACEP的振幅并不完全与AP和BSEP呈同步性改变;在高压氧下约半数动物的ACEP振幅增高,但其余动物的却呈现减低或无明显改变。这可能反映皮层对高压氧较为敏感,而且个体间敏感程度又不相同。实验结果提示,在两个绝对压下呼吸高压氧1小时对改善听觉系统的功能是有益的。     

间歇性排气嗓声辐射特性的研究

将排气噪声分为三类,研究了间歇性排气过程中的空气动力学和噪声特性,建立了间歇性排气噪声中的单极子源和四极子源所产生噪声的声压级表达式。对气路系统中各参数对噪声的影响进行了全面深入的研究。     

Tuning Aggregation Behavior of Polymer Donor via Molecular-Weight Control for Achieving 17.1％ Efficiency Inverted Polymer Solar Cells

Main observation and conclusion Recently,the polymer solar cells (PSCs) based on the PM6 and small molecular acceptor (SMA) Y6 have attracted considerable atten...     

Surface modification boosts exciton extraction in confined layered structure for selective oxidation reaction

Science China Chemistry - Extracting photogenerated species from bulk to surface is an essential process for gaining efficient semiconductor-based photocatalysis. However, compared with charged...