Regioselective Nickel‐Catalyzed Hydroarylation of gem‐Difluoroalkenes for the Synthesis of the ArCF2−${\rm{ArCF}}_{{2}^{-}}$ MoietyChen, Xiangyu; Wu, Yaxing; Zhang, Ruitong; Wang, Fei; Chen, Chao
doi: 10.1002/anie.202424714pmid: 40162812
The incorporation of fluorine and fluorinated functional groups into organic molecules alters their physicochemical properties, thereby facilitating the advancement of novel therapeutics, agricultural chemicals, biological probes, and materials. Nevertheless, there remains a deficiency of methodologies for the catalytic synthesis of certain significant fluorine‐containing groups, such as ArCF2−${\rm{ArCF}}_{{2}^{-}}$, under mild conditions utilizing earth‐abundant metals. Herein, we report a method for the regioselective hydroarylation of gem‐difluoroalkenes under mild conditions with the aid of Ni─H intermediate catalysis, which is capable of efficiently synthesizing compounds containing the ArCF2−${\rm{ArCF}}_{{2}^{-}}$ structural motifs and possesses good functional group tolerance.
Unveiling the Influence of Dehydrofluorination of Poly(vinylidene fluoride) Binder on the Failure of Graphite Anode in Potassium‐ion BatteriesYan, Yangtian; Hu, Junyang; Gao, Yueteng; Hou, Tingzheng; Zhang, Biao; Liang, Jin; Li, Baohua; Kang, Feiyu; Zhai, Dengyun
doi: 10.1002/anie.202502872pmid: 40140636
The poly(vinylidene fluoride) (PVDF) binder has been successfully employed in lithium‐ion batteries (LIBs), but it unexpectedly exhibits detrimental effects on the anode performance in potassium‐ion batteries (PIBs). The PVDF‐based graphite electrode shows a low Coulombic efficiency and even fails to maintain the electrode integrity after several cycles in the 0.8 M KPF6 ethylene carbonate/diethyl carbonate electrolyte. In this study, we unveil that the dehydrofluorination reaction of PVDF initiated by potassium ethoxide may be the key factor causing the above issues. The dehydrofluorination not only disables the binder but also releases detrimental ethanol into the electrolyte. The released ethanol can dissolve the organic components of solid electrolyte interphase (SEI) and deplete the potassium resource, thereby resulting in a reduction of Coulombic efficiency and a more severe accumulation of SEI. The crowding of more accumulated SEI coupled with the large volume expansion of intercalated graphite results in the failure of PVDF‐based graphite electrodes. This fundamental finding may provide a deeper insight into the failure mechanism of PVDF as a binder in PIBs, and meanwhile, give valuable guidance for the use of PVDF in battery communities containing sodium‐ion batteries and LIBs.
Enhancing Circularly Polarized Luminescence of Anthraquinones via J‐Type Supramolecular PolymerizationGao, Laiwei; Liao, Rui; Ao, Lei; Zhang, Yifei; Jin, Jianan; Wang, Feng
doi: 10.1002/anie.202505776pmid: 40170265
Circularly
polarized luminescence materials based on cost‐effective point‐chiral luminophores are highly desirable; however, their performance is often hindered by weak exciton–chirality coupling between the luminophore and its adjacent stereocenters. Here, we introduce J‐type supramolecular polymerization as an effective strategy to address this challenge. By attaching amide groups to point‐chiral anthraquinone luminophores, the formation of directional hydrogen bonds facilitates efficient chirality transfer from peripheral stereocenters to anthraquinones, resulting in supramolecular polymers with amplified chiroptical asymmetry. More importantly, the incorporation of acetylene spacers reduces torsional angle of the anthraquinone core compared to the nonacetylene control compound (1.81° versus 33.4°), promoting J‐aggregation and increasing emission intensity. This structural optimization enables the supramolecular polymers to achieve a circularly polarized luminescence brightness of 13.8 M⁻¹cm⁻¹, marking a significant advancement in point‐chiral luminophore systems. Furthermore, the integration of Förster resonance energy transfer into these supramolecular polymers allows for the fabrication of color‐tunable circularly polarized electroluminescent devices. Overall, J‐type supramolecular polymerization represents a promising approach for developing high‐performance chiroptical materials by simultaneously optimizing emission dissymmetry and quantum efficiency.
Isolable Three‐Coordinate Base‐Stabilized Alumylene: A Precursor of Persistent Acceptor‐Free Monomeric Aluminum OxideBaeza, José Miguel León; Xu, Huihui; Takahashi, Shintaro; Baceiredo, Antoine; Guerrero, Rene Segundo Rojas; Hashizume, Daisuke; Saffon‐Merceron, Nathalie; Branchadell, Vicenç; Kato, Tsuyoshi
doi: 10.1002/anie.202505181pmid: 40162864
An isolable monomeric alumylene 2 stabilized by two donating ligands (phosphine and NHC) has been synthesized. Experimental and theoretical analysis confirm that the NHC ligand in 2 is labile and reversibly dissociates from the AlI center above −20 °C. Of particular interest, despite being thermodynamically stabilized by two donor ligands, alumylene complex 2 exhibits a high reactivity with a considerably higher nucleophilicity compared to the monophosphine‐ligated complex 5. It is interesting to note that 2 reacts immediately with N2O at −90 °C, allowing the synthesis of bis‐ligated aluminum oxide 15, which is stable up to −70 °C.
Asymmetric Synthesis of Noradamantane Scaffolds via Diphenylprolinol Silyl Ether‐Mediated Domino Michael/Epimerization/Michael (or Aldol)/1,2‐Addition ReactionsDaskalakis, Konstantinos; Umekubo, Nariyoshi; Indu, Satrajit; Kawauchi, Genki; Taniguchi, Tohru; Monde, Kenji; Hayashi, Yujiro
doi: 10.1002/anie.202500378pmid: 40122692
Topologically unique chiral noradamantanes are synthesized using a diphenylprolinol silyl ether‐mediated domino Michael/epimerization/Michael/1,2‐addition or Michael/epimerization/aldol/1,2‐addition reaction with excellent enantioselectivity in a single reaction vessel. Three carbon–carbon bonds are formed, and six chiral centers, including one all‐carbon quaternary center, are generated, five of which are fully controlled. These functionalized noradamantanes are 3D, cage‐like molecules that can serve as valuable chiral building blocks for drug design.
Hierarchical Optical Waveguides Based on Serpentine‐Like Organic Pseudo‐Plastic Crystals that Mimic Neural NetworksKumar, Avulu Vinod; Rohullah, Mehdi; Chosenyah, Melchi; Sindhuja, Gaddam; Chandrasekar, Rajadurai
doi: 10.1002/anie.202502122pmid: 40103290
Optical components and circuits for signal generation and processing are essential for artificial neural networks (ANNs). We present an interconnected, four‐layered organic crystal optical waveguide architecture that mimics an ANN. This structure is constructed from pseudo‐plastic organic crystals of (E)‐1‐(((5‐methylpyridin‐2‐yl)imino)methyl)naphthalene‐2‐ol (MPyIN) using an atomic force microscopy (AFM) cantilever tip‐based micromanipulation technique. By strategically selecting four MPyIN crystal waveguides of varying lengths, bending them into serpentine‐like forms, and integrating them hierarchically, we create interconnected, neuron‐like optical waveguides with six optical synapses. These synapses enable parallel transmission of passive optical signals through evanescent coupling across multiple paths within the waveguides. The feedforward mechanism allows the synapses to split the input optical signal into four diverging signals with different magnitudes. Certain outputs deliver mixed passive and active signals due to diverging and converging optical paths. This hierarchical, ANN‐like architecture offers a foundation for developing smart optical neural networks using multiple emissive and phase‐changing organic crystals.
Activating Interfacial Ion Exchange in Composite Electrolytes to Realize High‐Rate and Long‐Cycling Solid‐State Lithium BatteriesZhu, Qiannan; Yang, Ke; Chen, Likun; An, Xufei; Guo, Shaoke; Li, Yuhang; Ma, Yuetao; Cao, Yidan; Liu, Ming; He, Yan‐Bing
doi: 10.1002/anie.202425221pmid: 40152270
Composite solid electrolytes (CSEs) are promising candidates for solid‐state lithium metal batteries. However, the poor cross‐phase Li+ transport restricts the rate performance and cycle life of the batteries. Herein, we revealed the Li+ percolation behavior in poly(vinylidene fluoride) (PVDF)‐based CSEs with Li6.4La3Zr1.4Ta0.6O12 filler. The de‐coordination barrier from Li+ clusters determines interfacial Li+ transport capability. We then employed a designed N‐methyl‐2,2,2‐trifluoroacetamide (NMTFA) ligand to lower the de‐coordination energy and activate interfacial Li+ exchange. The ionic conductivity is therefore increased from 3.32 × 10−4 to 7.30 × 10−4 S cm−1. By tracking the 6Li and 7Li substitution process, it was identified that the proportion of interfacial Li+ transport increases from 11% to 26%. The NMTFA also contributes to the formation of inorganic‐rich interphases with electrodes. As a result, the Li||LiNi0.8Co0.1Mn0.1O2 solid‐state batteries exhibit ultra‐long lifespans of 2400, 3000, and 10 000 times at 2, 5, and 10C, respectively, as well as achieve 1000 cycles at 50 °C and 300 cycles at −30 °C. This work highlights the critical role of interfacial Li+ transport for the CSEs with “polymer‐Li+ clusters‐filler” configuration to realize high‐rate and long‐cycling solid‐state lithium batteries.