Dr. Xinyu Guan  Fengqian Chen  Prof. Dr. Shilun Qiu  Prof. Dr. Qianrong Fang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(3):e202213203

Three-dimensional covalent organic frameworks (3D COFs) with spatially periodic networks demonstrate significant advantages over their 2D counterparts, including enhanced specific surface areas, interconnected channels, and more sufficiently exposed active sites. Nevertheless, research on these materials has met an impasse due to serious problems in crystallization and stability, which must be solved for practical applications. In this Minireview, we first summarize some strategies for preparing functional 3D COFs, including crystallization techniques and functionalization methods. Hereafter, applications of these functional materials are presented, covering adsorption, separation, catalysis, fluorescence, sensing, and batteries. Finally, the future challenges and perspectives for the development of 3D COFs are discussed.  相似文献   

    

Yang Hua  Dr. Wei Bai  Shengnan Dai  Rongjie He  Dr. Pengfei Nan  Liang Sun  Prof. Jiong Yang  Prof. Bo Sun  Prof. Binghui Ge  Prof. Chong Xiao  Prof. Yi Xie 《Angewandte Chemie (International ed. in English)》2023,62(27):e202303081

Currently, the efforts to find materials with high κ anisotropy ratios mainly focus on layered materials, however, the limited quantity and lower workability comparing to non-layered ones boost the exploration of non-layered materials with high κ anisotropy ratios. Here, taking PbSnS₃, a typical non-layered orthorhombic compound, as an example, we propose that maldistribution of chemical bond strength can lead to large anisotropy of κ in non-layered materials. Our result reveals that the maldistribution of Pb−S bonds lead to obvious collective vibrations of dioctahedron chain units, resulting in an anisotropy ratio up to 7.1 at 200 K and 5.5 at 300 K, respectively, which is one of the highest ever reported in non-layered materials and even surpasses many classical layered materials such as Bi₂Te₃ and SnSe. Our findings can not only broaden the horizon for exploring high anisotropic κ materials but also provide new opportunities for the application of thermal management.  相似文献   

    

Jiahui Zeng  Yu Fu  Yue Wu  Shanshan Wang  Wenxiang Zhang  Prof. Heping Ma 《Angewandte Chemie (International ed. in English)》2023,62(42):e202310235

Xe is an ideal anesthetic gas, but it has not been widely used in practice due to its high cost and low output. Closed-circuit Xe recovery and recycling is an economically viable method to ensure adequate supply in medical use. Herein, we design an innovative way to recover Xe by using a stable fluorinated metal-organic framework (MOF) NbOFFIVE-1-Ni to eliminate CO₂ from moist exhaled anesthetic gases. Unlike other Xe recovery MOFs with low Xe/CO₂ selectivity (less than 10), NbOFFIVE-1-Ni could achieve absolute molecular sieve separation of CO₂/Xe with excellent CO₂ selectivity (825). Mixed-gas breakthrough experiments assert the potential of NbOFFIVE-1-Ni as a molecular sieve adsorbent for the effective and energy-efficient removal of carbon dioxide with 99.16 % Xe recovery. Absolute CO₂/Xe separation in NbOFFIVE-1-Ni makes closed-circuit Xe recovery and recycling can be easily realized, demonstrating the potential of NbOFFIVE-1-Ni for important anesthetic gas regeneration under ambient conditions.  相似文献   

    

Dr. Xuelin Yao  Dr. Heng Zhang  Fanmiao Kong  Dr. Antoine Hinaut  Dr. Rémy Pawlak  Prof. Dr. Masanari Okuno  Dr. Robert Graf  Dr. Peter N. Horton  Prof. Dr. Simon J. Coles  Prof. Dr. Ernst Meyer  Prof. Dr. Lapo Bogani  Prof. Dr. Mischa Bonn  Prof. Dr. Hai I. Wang  Prof. Dr. Klaus Müllen  Prof. Dr. Akimitsu Narita 《Angewandte Chemie (International ed. in English)》2023,62(46):e202312610

Structurally defined graphene nanoribbons (GNRs) have emerged as promising candidates for nanoelectronic devices. Low band gap (<1 eV) GNRs are particularly important when considering the Schottky barrier in device performance. Here, we demonstrate the first solution synthesis of 8-AGNRs through a carefully designed arylated polynaphthalene precursor. The efficiency of the oxidative cyclodehydrogenation of the tailor-made polymer precursor into 8-AGNRs was validated by FT-IR, Raman, and UV/Vis-near-infrared (NIR) absorption spectroscopy, and further supported by the synthesis of naphtho[1,2,3,4-ghi]perylene derivatives ( 1 and 2 ) as subunits of 8-AGNR , with a width of 0.86 nm as suggested by the X-ray single crystal analysis. Low-temperature scanning tunneling microscopy (STM) and solid-state NMR analyses provided further structural support for 8-AGNR . The resulting 8-AGNR exhibited a remarkable NIR absorption extending up to ∼2400 nm, corresponding to an optical band gap as low as ∼0.52 eV. Moreover, optical-pump TeraHertz-probe spectroscopy revealed charge-carrier mobility in the dc limit of ∼270 cm² V⁻¹ s⁻¹ for the 8-AGNR .  相似文献   

    

Shenghao Li  Jing Lin  Mareen Schaller  Sylvio Indris  Xin Zhang  Torsten Brezesinski  Ce-Wen Nan  Shuo Wang  Florian Strauss 《Angewandte Chemie (International ed. in English)》2023,62(50):e202314155

Superionic solid electrolytes (SEs) are essential for bulk-type solid-state battery (SSB) applications. Multicomponent SEs are recently attracting attention for their favorable charge-transport properties, however a thorough understanding of how configurational entropy (ΔS_conf) affects ionic conductivity is lacking. Here, we successfully synthesized a series of halogen-rich lithium argyrodites with the general formula Li_5.5PS_4.5Cl_xBr_1.5-x (0≤x≤1.5). Using neutron powder diffraction and ³¹P magic-angle spinning nuclear magnetic resonance spectroscopy, the S²⁻/Cl⁻/Br⁻ occupancy on the anion sublattice was quantitatively analyzed. We show that disorder positively affects Li-ion dynamics, leading to a room-temperature ionic conductivity of 22.7 mS cm⁻¹ (9.6 mS cm⁻¹ in cold-pressed state) for Li_5.5PS_4.5Cl_0.8Br_0.7 (ΔS_conf=1.98R). To the best of our knowledge, this is the first experimental evidence that configurational entropy of the anion sublattice correlates with ion mobility. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors by tailoring the degree of compositional complexity. Moreover, the Li_5.5PS_4.5Cl_0.8Br_0.7 SE allowed for stable cycling of single-crystal LiNi_0.9Co_0.06Mn_0.04O₂ (s-NCM90) composite cathodes in SSB cells, emphasizing that dual-substituted lithium argyrodites hold great promise in enabling high-performance electrochemical energy storage.  相似文献   

    

Dr. Jikuan Qiu  Chang Xu  Xianhui Xu  Yingjie Zhao  Prof. Dr. Yang Zhao  Dr. Yuling Zhao  Prof. Dr. Jianji Wang 《Angewandte Chemie (International ed. in English)》2023,62(17):e202300459

Utilizing weak interactions to effectively recover and separate precious metals in solution is of great importance but the practice remains a challenge. Herein, we report a novel strategy to achieve precise recognition and separation of gold by regulating the hydrogen-bond (H-bond) nanotrap within the pore of covalent organic frameworks (COFs). It is found that both COF-HNU25 and COF-HNU26 can efficiently capture Au^III with fast kinetics, high selectivity, and uptake capacity. In particular, the COF-HNU25 with the high density of H-bond nanotraps exhibits an excellent gold uptake capacity of 1725 mg g⁻¹, which is significantly higher than that (219 mg g⁻¹) of its isostructural COF (COF-42) without H-bond nanostrap in the pores. Importantly, the uptake capacity is strongly correlated to the number of H-bonds between phenolic OH in the COF and [AuCl₄]⁻ in water, and multiple H-bond interactions are the key driving force for the excellent gold recovery and reusability of the adsorbent.  相似文献   

    

Younghun Kim  Heechan Kim  Dr. Jung Bae Son  Dr. Michael Filatov  Prof. Dr. Cheol Ho Choi  Prof. Dr. Nam Ki Lee  Prof. Dr. Dongwhan Lee 《Angewandte Chemie (International ed. in English)》2023,62(20):e202302107

Molecular emitters simultaneously generating light at different wavelengths have wide applications. With a small molecule, however, it is challenging to realize two independent radiative pathways. We invented the first examples of dual-emissive single-benzene fluorophores (SBFs). Two emissive tautomers are generated by synthetic modulation of the hydrogen bond acidity, which opens up pathways for excited-state proton transfer. White light is produced by a delicate balance between the energy and intensity of the emission from each tautomer. We show that the excited-state antiaromaticity of the benzene core itself dictates the proton movements driving the tautomer equilibrium. Using this simple benzene platform, a fluorinated SBF was synthesized with a record high solubility in perfluorocarbon solvents. White light-emitting devices and multicolor imaging of perfluorocarbon nanodroplets in live cells demonstrate the practical utility of these molecules.  相似文献   

    

Caitlin E. Shields  Dr. Xue Wang  Dr. Thomas Fellowes  Rob Clowes  Dr. Linjiang Chen  Prof. Graeme M. Day  Prof. Anna G. Slater  Dr. John W. Ward  Dr. Marc A. Little  Prof. Andrew I. Cooper 《Angewandte Chemie (International ed. in English)》2023,62(34):e202303167

Hydrogen-bonded organic frameworks (HOFs) with low densities and high porosities are rare and challenging to design because most molecules have a strong energetic preference for close packing. Crystal structure prediction (CSP) can rank the crystal packings available to an organic molecule based on their relative lattice energies. This has become a powerful tool for the a priori design of porous molecular crystals. Previously, we combined CSP with structure-property predictions to generate energy-structure-function (ESF) maps for a series of triptycene-based molecules with quinoxaline groups. From these ESF maps, triptycene trisquinoxalinedione (TH5) was predicted to form a previously unknown low-energy HOF (TH5-A) with a remarkably low density of 0.374 g cm⁻³ and three-dimensional (3D) pores. Here, we demonstrate the reliability of those ESF maps by discovering this TH5-A polymorph experimentally. This material has a high accessible surface area of 3,284 m² g⁻¹, as measured by nitrogen adsorption, making it one of the most porous HOFs reported to date.  相似文献   

    

Seok J. Lee  Shane G. Telfer 《Angewandte Chemie (International ed. in English)》2023,62(44):e202306341

Metal-organic frameworks (MOFs) are constructed from metal ions or clusters and organic linkers. Typical MOFs are rather simple, comprising just one type of joint and linker. An additional degree of structural complexity can be introduced by using multiple different components that are assembled into the same framework In the early days of MOF chemistry, conventional wisdom held that attempting to prepare frameworks starting from such a broad set of components would lead to multiple different phases. However, this review highlights how this view was mistaken and frameworks comprising multiple different components can be deliberately designed and synthesized. When coupled to structural order and periodicity, the presence of multiple components leads to exceptional functional properties that can be understood at the atomic level.  相似文献   

    

Claudius Lupfer  Sebastian Seitel  Oliver Skarsetz  Andreas Walther 《Angewandte Chemie (International ed. in English)》2023,62(41):e202309236

Cellular organisms possess intricate mechano-adaptive systems that enable them to sense forces and process them with (bio)chemical circuits for functional adaptation. Inspired by such processes, this study introduces a hydrogel system capable of mechanically activated and chemically transduced self-destruction. Our judiciously designed hydrogels can mechanically generate radicals that are processed and amplified in a self-propagating radical de-crosslinking reaction, ultimately leading to mechanically triggered self-immolation. We put such systems to work in mechano-induced debonding, and in a bilayer actuator, where swelling-induced bending generates sufficient force for selective degradation of one layer, leading to autonomous self-regulation associated with unbending. Our work helps define design criteria for molecularly controlled adaptive and self-regulating materials with embodied mechano-chemical information processing, and showcases their potential for adhesives and soft robotics.  相似文献