A 3D Nanostructured Hydrogel‐Framework‐Derived High‐Performance Composite Polymer Lithium‐Ion Electrolyte

Solid‐state electrolytes have emerged as a promising alternative to existing liquid electrolytes for next generation Li‐ion batteries for better safety and stability. Of various types of solid electrolytes, composite polymer electrolytes exhibit acceptable Li‐ion conductivity due to the interaction between nanofillers and polymer. Nevertheless, the agglomeration of nanofillers at high concentration has been a major obstacle for improving Li‐ion conductivity. In this study, we designed a three‐dimensional (3D) nanostructured hydrogel‐derived Li_0.35La_0.55TiO₃ (LLTO) framework, which was used as a 3D nanofiller for high‐performance composite polymer Li‐ion electrolyte. The systematic percolation study revealed that the pre‐percolating structure of LLTO framework improved Li‐ion conductivity to 8.8×10^?5 S cm^?1 at room temperature.     

Mechanofluorochromic Carbon Nanodots: Controllable Pressure‐Triggered Blue‐ and Red‐Shifted Photoluminescence

Mechanofluorochromic materials, which change their photoluminescence (PL) colors in responding to mechanical stimuli, can be used as mechanosensors, security papers, and photoelectronic devices. However, traditional mechanofluorochromic materials can only be adjusted to a monotone direction upon the external stimuli. Controllable pressure‐triggered blue‐ and red‐shifted PL is reported for C‐dots. The origin of mechanofluorochromism (MFC) in C‐dots is interpreted based on structure–property relationships. The carbonyl group and the π‐conjugated system play key roles in the PL change of C‐dots under high pressure. As the pressure increases, the enhanced π–π stacking of the π‐conjugated system causes the red‐shift of PL, while the conversion of carbonyl groups eventually induces a blue‐shift. Together with their low toxicity, good hydrophilicity, and small size, the tunable MFC property would boost various potential applications of C‐dots.     

Dynamic Ultralong Organic Phosphorescence by Photoactivation

Smart materials with ultralong phosphorescence are rarely investigated and reported. Herein we report on a series of molecules with unique dynamic ultralong organic phosphorescence (UOP) features, enabled by manipulating intermolecular interactions through UV light irradiation. Our experimental data reveal that prolonged irradiation of single‐component organic phosphors of PCzT, BCzT, and FCzT under ambient conditions can activate UOP with emission lifetimes spanning from 1.8 to 1330 ms. These phosphors can also be deactivated back to their original states with short‐lived phosphorescence by UV irradiation for 3 h at room temperature or through thermal treatment. Additionally, the dynamic UOP was applied successfully for a visual anti‐counterfeiting application. These findings may provide unique insight into dynamic molecular motion for optical processing and expand the scope of smart‐response materials for broader applications.     

Solvent‐Dependent Asymmetric Synthesis of Alkynyl and Monofluoroalkenyl Isoindolinones by CpRhIII‐Catalyzed C−H Activation

The asymmetric synthesis of alkynyl and monofluoroalkenyl isoindolinones from N‐methoxy benzamides and α,α‐difluoromethylene alkynes is enabled by C?H activation with a chiral CpRh^III catalyst. Remarkably, product formation is solvent‐dependent; alkynyl isoindolinones are afforded in MeOH (up to 86 % yield, 99.6 % ee) whereas monofluoroalkenyl isoindolinones are generated in ⁱPrCN (up to 98:2 Z/E, 93 % yield, 86 % ee). Mechanistic studies revealed chiral allene and E‐configured alkenyl rhodium species as reaction intermediates. The latter is transformed into the corresponding Z‐configured monofluoroalkene upon protonation in the ⁱPrCN system and into an alkyne by an unusual anti β‐F elimination in the MeOH system. Notably, kinetic resolution processes occur in this reaction. Despite the moderate enantiocontrol for the formation of the chiral allene, the Z‐monofluoroalkenyl isoindolinones and alkynyl isoindolinones were obtained in good enantiopurities by one or two sequential kinetic resolution processes.     

Acid-promoted furan annulation and aromatization: An access to benzo[b]furan derivatives

An unprecedented PTSA-promoted furan annulation and aromatization in one pot has been developed. This process offers a simple and efficient synthetic route for the construction of various highly substituted benzo[b]furan derivatives, which are widely used not only in drug active molecules but also organic semiconductor and organic light-emitting devices. The preliminary mechanism study indicated this transformation proceeded sequentially via furan annulation and aromatization.     

Enantiomer-selective Living Polymerization of rac-Phenyl Isocyanide Using Chiral Palladium Catalyst

We report the polymerization of phenyl isocyanides with the chiral palladium(II) initiating system. The resulting polymers with optically active properties were obtained by polymerization of the racemic isocyanide monomer(rac-1), and enantiomerically unbalanced polymerization of the monomer was found, providing substantial evidence for the enantiomer-selective polymerization of rac-1 mediated through chiral catalyst. A comparison between the enantiomerically pure monomers, 4-isocyanobenzoyl-L-alanine decyl ester(1 s) and 4-isocyanobenzoyl-D-alanine decyl ester(1 r), revealed a drastic discrepancy in the reactivity ratio of their homopolymerizations.It turned out that the monomer reactivity ratio of 1 s was higher than that of 1 r with chiral ligands. The results clearly demonstrated the inclination for incorporation of the 1 s enantiomer during the polymerization process and thus resulted in the enantiomer-selective polymerization in this system. The effects of the catalyst chirality on the optically active properties of polymerization were investigated,and it was concluded that the formation of higher-ordered conformation with a handed helicity might be attributed to the chiral induction of chiral palladium(II) catalyst. Moreover, the polymers obtained through the enantiomer-selective polymerization of the enantiomerically pure monomer were with a significant improvement of the optical activity if the chirality of the monomer and the catalyst matched with each other.     

丝网印刷柔性电子器件

有机电子器件的主要优势之一是溶液可处理性,这使得可以通过多种印刷方法制备有机电子器件。丝网印刷作为一种十分成熟的印刷方法,被广泛应用于微电子器件的制备。本文主要从丝网印刷的组成、影响丝网印刷精密度的因素以及丝网印刷在场效应晶体管、太阳能电池、有机发光二极管等柔性电子器件制备中的应用分别作以介绍,并对目前丝网印刷在印刷柔性电子器件中存在的困难和挑战作以总结。     

石墨烯在复合热电材料中的应用

热电材料是一种可以实现热能与电能之间直接相互转换的功能材料,在温差发电和热电制冷方面具有广阔的应用空间。石墨烯是一种单原子层厚度的二维碳材料,具有特殊的晶体结构和优异的物理化学性质。大量研究表明石墨烯优异的电学性能、超大的比表面积以及多样的边界结构有利于材料电、热性能的协同调控,使其在热电领域有较大的应用潜力。本文结合热电材料的性能特点,从石墨烯的结构与性能入手,综述了石墨烯自身作为热电材料时结构与性能的优化关系,并总结归纳了石墨烯与Bi₂Te₃、CoSb₃等传统无机热电材料以及与导电高分子热电材料构成纳米复合块体和薄膜时,对材料结构与热电性能的影响,并结合现存的问题对石墨烯在热电领域中的应用进行了展望。     

手性杯芳烃及其超分子手性

杯芳烃是由苯酚单元通过亚甲基连接而成的空腔型分子,具有衍生位点多,构象丰富等特点,被称为第三代主体分子。在分子层次,依手性因素的结构特点不同,可将手性杯芳烃分为具有手性亚单元的杯芳烃、固有手性杯芳烃和桥手性杯芳烃。在超分子层次,杯芳烃自身或杯芳烃与其他分子或离子在溶液中、晶态中或二维表面可通过非共价键力形成多种拓扑结构的纳米手性聚集体。研究手性杯芳烃和基于杯芳烃的超分子手性组装体的合成、结构和性能,不仅在理解手性起源、手性结构等方面具有理论意义,而且有望获得以分子识别为基础的手性传感器、手性催化剂、手性分离材料、手性载体和手性纳米材料。本文综述近十年来有代表性的分子手性杯芳烃和以杯芳烃为组分的超分子手性聚集体的设计、合成、结构和功能。着重展示杯芳烃骨架在形成新颖分子手性和超分子手性上的优势,以及杯芳烃单元在实现特定功能如手性识别时发挥的作用。相信随着杯芳烃合成技术和杯芳烃超分子设计的发展,必将进一步发挥杯芳烃的结构优势,涌现出更多性能优异的手性杯芳烃功能分子和超分子手性杯芳烃功能材料。     

杂环烯酮缩胺:构筑分子多样性稠杂环化合物的合成先导分子

杂环烯酮缩胺（HKAs）是一类构建分子多样性稠杂环化合物的多功能合成砌块,已被广泛应用于构筑多种多样的类天然杂环化合物和合成药物中。随着杂环烯酮缩胺研究的深入开展,其作为双亲核试剂与多种亲电底物反应取得了较大的进展。本文将基于HKAs的结构特征、反应性能,对以HKAs及1,1-烯二胺为合成子构建各种类型具有潜在生物活性的类天然多环稠杂环化合物进行综述。