@article{60552, abstract = {{AbstractThe incorporation of heteroatoms into the framework of polycyclic aromatic hydrocarbons (PAHs), in particular of nitrogen to yield polycyclic aromatic nitrogen heterocycles (PANHs), has been proposed for both astronomical and combustion environments, but no suitable precursors and pathways have been found. Analogous pathways to PAH formation are kinetically or energetically inhibited in the presence of a nitrogen heteroatom. We report on the reaction of phenylnitrene (3PhN, c‐C6H5N) with resonance‐stabilized propargyl radicals (C3H3) and find that the association reaction bifurcates depending on the orientation of the attacking propargyl radical and yields multiple isomeric products. Among them, we identify the condensed‐ring quinoline and conclude that nitrenes are viable candidates to drive the formation of PANHs.}}, author = {{Arns, Rahel and McClish, Rory and Hemberger, Patrick and Bodi, Andras and Bouwman, Jordy and Kasper, Tina and Schleier, Domenik}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, publisher = {{Wiley}}, title = {{{Is Phenylnitrene a Missing Link in the Formation of Polycyclic Aromatic Nitrogen Heterocycles?}}}, doi = {{10.1002/anie.202503940}}, year = {{2025}}, } @article{60551, abstract = {{AbstractThe incorporation of heteroatoms into the framework of polycyclic aromatic hydrocarbons (PAHs), in particular of nitrogen to yield polycyclic aromatic nitrogen heterocycles (PANHs), has been proposed for both astronomical and combustion environments, but no suitable precursors and pathways have been found. Analogous pathways to PAH formation are kinetically or energetically inhibited in the presence of a nitrogen heteroatom. We report on the reaction of phenylnitrene (3PhN, c‐C6H5N) with resonance‐stabilized propargyl radicals (C3H3) and find that the association reaction bifurcates depending on the orientation of the attacking propargyl radical and yields multiple isomeric products. Among them, we identify the condensed‐ring quinoline and conclude that nitrenes are viable candidates to drive the formation of PANHs.}}, author = {{Arns, Rahel and McClish, Rory and Hemberger, Patrick and Bodi, Andras and Bouwman, Jordy and Kasper, Tina and Schleier, Domenik}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, publisher = {{Wiley}}, title = {{{Is Phenylnitrene a Missing Link in the Formation of Polycyclic Aromatic Nitrogen Heterocycles?}}}, doi = {{10.1002/anie.202503940}}, year = {{2025}}, } @article{61821, abstract = {{AbstractControlling the surface orientation of DNA origami nanostructures (DON) is crucial for applications in nanotechnology and materials science. While previous work utilized various DON modifications, simple methods for controlling their landing orientation remain scarce. Here, we demonstrate a straightforward approach to control the adsorption orientation of chiral double‐L (CDL) DON on mica by tuning magnesium ion (Mg2⁺) concentration and exploiting global shape distortions. Using atomic force microscopy (AFM), we analyzed the resulting distribution of the mirror‐image orientations, referred to as S and Z orientations, at both buffer/mica and air/mica interfaces and identified conditions resulting in homogenous CDL orientation of 100% S. These results demonstrate how DON conformation and ionic environments influence DON orientation, offering insights for precise nanostructure deposition.}}, author = {{Velpula, Gangamallaiah and Tomm, Emilia and Shen, Boxuan and Mali, Kunal S. and Keller, Adrian Clemens and De Feyter, Steven}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, publisher = {{Wiley}}, title = {{{Breaking of the Up‐Down Symmetry of DNA Origami on a Solid Substrate}}}, doi = {{10.1002/anie.202507613}}, year = {{2025}}, } @article{62654, abstract = {{Abstract Cationic gold catalyzed acetylene hydrochlorination represents a classical landmark in eliminating global mercury pollution, but their sustainable implementation is hindered by acetylene‐dependence design criteria and high operating temperatures. Herein, a platform of carbon‐supported single‐atoms Au catalysts (Au/BC and Au/NC) with polarized charge characteristics are developed via engineering Au sites with hosted B, N configurations. The negatively charged Au/BC catalyst unlocks the low‐temperature inactivity (413–423K) of the Au/NC catalyst while exhibiting superior catalytic performance in the 433–473K operating temperature range. We confirm that the classical scaling relationships on acetylene can be broken by narrowing the adsorption capacity between acetylene and HCl on Au δ⁻ sites via facilitating the back‐donation of d electrons into the antibonding orbitals of acetylene. Prolonging the durability of Au catalysts is achieved through preceding an additional robust Au δ⁻ → Au δ⁺ cycle prior to the classic Au δ⁺ → Au 0 route. This work opens a promising avenue for low temperature vinyl chloride production. }}, author = {{Li, Chun and Liu, Ruoting and Zhang, Zilong and Zuo, Fangmin and Jiang, Tingting and Zhang, Haifeng and Wang, Bolin and Lopez Salas, Nieves}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, number = {{29}}, publisher = {{Wiley}}, title = {{{Engineering Charge Polarized Au Sites for Low‐Temperature Acetylene Hydrochlorination}}}, doi = {{10.1002/anie.202501370}}, volume = {{64}}, year = {{2025}}, } @article{63989, abstract = {{We introduce the first mechanochemical cyclotrimerization of nitriles, a facile strategy for synthesizing triazine-containing molecules and materials, overcoming challenges related to carbonization and solubility. Conducting this solid-state approach in a mixer ball mill with 4-Methylbenzonitrile, we synthesize Tris(4-methylphenyl)-1,3,5-triazine quantitatively in as little as 90 minutes. Just as fast, this mechanochemical method facilitates the synthesis of the covalent triazine framework CTF-1 using 1,4 Dicyanobenzene. Material characterization confirms its porous (650 m2 g-1) and crystalline nature. Adjusting the induced mechanical energy allows control over the obtained stacking conformation of the resulting CTFs - from a staggered AB arrangement to an eclipsed AA stacking conformation. Finally, a substrate scope demonstrates the versatility of this approach, successfully yielding various CTFs. This work presents, for the first time, the mechanochemical cyclotrimerization of nitriles. Utilizing Trifluoromethanesulfonic acid and a ball mill, both small molecules and large organic frameworks could be obtained. Screening the reaction of 1,4-Dicyanobenzene by various parameters, such as reaction time, frequency, or temperature, significant impacts on the porosity of the polymer and its crystallinity were revealed. image}}, author = {{Hutsch, S. and Leonard, A. and Grätz, S. and Höfler, M. V. and Gutmann, Torsten and Borchardt, L.}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie-International Edition}}, title = {{{Mechanochemical Cyclotrimerization: A Versatile Tool to Covalent Organic Frameworks with Tunable Stacking Mode}}}, doi = {{10.1002/anie.202403649}}, year = {{2024}}, } @article{61848, abstract = {{AbstractUnderstanding how water interacts with nanopores of carbonaceous electrodes is crucial for energy storage and conversion applications. A high surface area of carbonaceous materials does not necessarily need to translate to a high electrolyte‐solid interface area. Herein, we study the interaction of water with nanoporous C1N1 materials to explain their very low specific capacitance in aqueous electrolytes despite their high surface area. Water was used to probe chemical environments, provided by pores of different sizes, in 1H MAS NMR experiments. We observe that regardless of their high hydrophilicity, only a negligible portion of water can enter the nanopores of C1N1, in contrast to a reference pure carbon material with a similar pore structure. The common paradigm that water easily enters hydrophilic pores does not apply to C1N1 nanopores below a few nanometers. Calorimetric and sorption experiments demonstrated strong water adsorption on the C1N1 surface, which restricts water mobility across the interface and impedes its penetration into the nanopores.}}, author = {{Lamata‐Bermejo, Irene and Keil, Waldemar and Nolkemper, Karlo and Heske, Julian and Kossmann, Janina and Elgabarty, Hossam and Wortmann, Martin and Chorążewski, Mirosław and Schmidt, Claudia and Kühne, Thomas D. and López‐Salas, Nieves and Odziomek, Mateusz}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, number = {{50}}, publisher = {{Wiley}}, title = {{{Understanding the Wettability of C1N1 (Sub)Nanopores: Implications for Porous Carbonaceous Electrodes}}}, doi = {{10.1002/anie.202411493}}, volume = {{63}}, year = {{2024}}, } @article{62660, abstract = {{AbstractUnderstanding how water interacts with nanopores of carbonaceous electrodes is crucial for energy storage and conversion applications. A high surface area of carbonaceous materials does not necessarily need to translate to a high electrolyte‐solid interface area. Herein, we study the interaction of water with nanoporous C1N1 materials to explain their very low specific capacitance in aqueous electrolytes despite their high surface area. Water was used to probe chemical environments, provided by pores of different sizes, in 1H MAS NMR experiments. We observe that regardless of their high hydrophilicity, only a negligible portion of water can enter the nanopores of C1N1, in contrast to a reference pure carbon material with a similar pore structure. The common paradigm that water easily enters hydrophilic pores does not apply to C1N1 nanopores below a few nanometers. Calorimetric and sorption experiments demonstrated strong water adsorption on the C1N1 surface, which restricts water mobility across the interface and impedes its penetration into the nanopores.}}, author = {{Lamata‐Bermejo, Irene and Keil, Waldemar and Nolkemper, Karlo and Heske, Julian and Kossmann, Janina and Elgabarty, Hossam and Wortmann, Martin and Chorążewski, Mirosław and Schmidt, Claudia and Kühne, Thomas D. and Lopez Salas, Nieves and Odziomek, Mateusz}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, number = {{50}}, publisher = {{Wiley}}, title = {{{Understanding the Wettability of C1N1 (Sub)Nanopores: Implications for Porous Carbonaceous Electrodes}}}, doi = {{10.1002/anie.202411493}}, volume = {{63}}, year = {{2024}}, } @article{35694, author = {{Köring, Laura and Stepen, Arne and Birenheide, Bernhard and Barth, Simon and Leskov, Maxim and Schoch, Roland and Krämer, Felix and Breher, Frank and Paradies, Jan}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, publisher = {{Wiley}}, title = {{{Boron‐Centered Lewis Superacid through Redox‐Active Ligands: Application in C–F and S–F Bond Activation}}}, doi = {{10.1002/anie.202216959}}, year = {{2023}}, } @article{42878, author = {{Köring, Laura and Stepen, Arne and Birenheide, Bernhard and Barth, Simon and Leskov, Maxim and Schoch, Roland and Krämer, Felix and Breher, Frank and Paradies, Jan}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, publisher = {{Wiley}}, title = {{{Boron‐Centered Lewis Superacid through Redox‐Active Ligands: Application in C−F and S−F Bond Activation}}}, doi = {{10.1002/anie.202301632}}, year = {{2023}}, } @article{44116, abstract = {{Faradaic reactions including charge transfer are often accompanied with diffusion limitation inside the bulk. Conductive two-dimensional frameworks (2D MOFs) with a fast ion transport can combine both - charge transfer and fast diffusion inside their porous structure. To study remaining diffusion limitations caused by particle morphology, different synthesis routes of Cu-2,3,6,7,10,11-hexahydroxytriphenylene (Cu3(HHTP)2), a copper-based 2D MOF, are used to obtain flake- and rod-like MOF particles. Both morphologies are systematically characterized and evaluated for redox-active Li+ ion storage. The redox mechanism is investigated by means of X-ray absorption spectroscopy, FTIR spectroscopy and in situ XRD. Both types are compared regarding kinetic properties for Li+ ion storage via cyclic voltammetry and impedance spectroscopy. A significant influence of particle morphology for 2D MOFs on kinetic aspects of electrochemical Li+ ion storage can be observed. This study opens the path for optimization of redox active porous structures to overcome diffusion limitations of Faradaic processes.}}, author = {{Wrogemann, Jens Matthies and Lüther, Marco Joes and Bärmann, Peer and Lounasvuori, Mailis and Javed, Ali and Tiemann, Michael and Golnak, Ronny and Xiao, Jie and Petit, Tristan and Placke, Tobias and Winter, Martin}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, number = {{26}}, pages = {{e202303111}}, publisher = {{Wiley}}, title = {{{Overcoming Diffusion Limitation of Faradaic Processes: Property‐Performance Relationships of 2D Conductive Metal‐Organic Framework Cu3(HHTP)2 for Reversible Lithium‐Ion Storage}}}, doi = {{10.1002/anie.202303111}}, volume = {{62}}, year = {{2023}}, } @article{46277, author = {{Sieland, Benedikt and Stahn, Marcel and Schoch, Roland and Daniliuc, Constantin and Spicher, Sebastian and Grimme, Stefan and Hansen, Andreas and Paradies, Jan}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, publisher = {{Wiley}}, title = {{{Dispersion Energy‐Stabilized Boron and Phosphorus Lewis Pairs}}}, doi = {{10.1002/anie.202308752}}, year = {{2023}}, } @article{35077, author = {{Liang, Qian and Ma, Xuekai and Long, Teng and Yao, Jiannian and Liao, Qing and Fu, Hongbing}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, number = {{9}}, publisher = {{Wiley}}, title = {{{Circularly Polarized Lasing from a Microcavity Filled with Achiral Single‐Crystalline Microribbons}}}, doi = {{10.1002/anie.202213229}}, volume = {{62}}, year = {{2023}}, } @article{62673, abstract = {{AbstractSelf‐templating is a facile strategy for synthesizing porous carbons by direct pyrolysis of organic metal salts. However, the method typically suffers from low yields (<4%) and limited specific surface areas (SSA<2000 m2 g−1) originating from low activity of metal cations (e.g., K+ or Na+) in promoting construction and activation of carbon frameworks. Here we use cesium acetate as the only precursor of oxo‐carbons with large SSA of the order of 3000 m2 g−1, pore volume approaching 2 cm3 g−1, tunable oxygen contents, and yields of up to 15 %. We unravel the role of Cs+ as an efficient promoter of framework formation, templating and etching agent, while acetates act as carbon/oxygen sources of carbonaceous frameworks. The oxo‐carbons show record‐high CO2 uptake of 8.71 mmol g−1 and an ultimate specific capacitance of 313 F g−1 in the supercapacitor. This study helps to understand and rationally tailor the materials design by a still rare organic solid‐state chemistry.}}, author = {{Li, Jiaxin and Kossmann, Janina and Zeng, Ke and Zhang, Kun and Wang, Bingjie and Weinberger, Christian and Antonietti, Markus and Odziomek, Mateusz and Lopez Salas, Nieves}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, number = {{26}}, publisher = {{Wiley}}, title = {{{When High‐Temperature Cesium Chemistry Meets Self‐Templating: Metal Acetates as Building Blocks of Unusual Highly Porous Carbons}}}, doi = {{10.1002/anie.202217808}}, volume = {{62}}, year = {{2023}}, } @article{35689, author = {{Wicker, Garrit and Zhou, Rundong and Schoch, Roland and Paradies, Jan}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, number = {{31}}, publisher = {{Wiley}}, title = {{{Sigmatropic [1,5] Carbon Shift of Transient C3 Ammonium Enolates}}}, doi = {{10.1002/anie.202204378}}, volume = {{61}}, year = {{2022}}, } @article{35691, author = {{Wicker, Garrit and Zhou, Rundong and Schoch, Roland and Paradies, Jan}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, number = {{31}}, publisher = {{Wiley}}, title = {{{Cover Picture: Sigmatropic [1,5] Carbon Shift of Transient C3 Ammonium Enolates (Angew. Chem. Int. Ed. 31/2022)}}}, doi = {{10.1002/anie.202207944}}, volume = {{61}}, year = {{2022}}, } @article{40555, author = {{Lepre, Enrico and Rat, Sylvain and Cavedon, Cristian and Seeberger, Peter H. and Pieber, Bartholomäus and Antonietti, Markus and Lopez Salas, Nieves}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, number = {{2}}, publisher = {{Wiley}}, title = {{{Catalytic Properties of High Nitrogen Content Carbonaceous Materials}}}, doi = {{10.1002/anie.202211663}}, volume = {{62}}, year = {{2022}}, } @article{40560, author = {{Tian, Zhihong and Zhang, Qingran and Thomsen, Lars and Gao, Nana and Pan, Jian and Daiyan, Rahman and Yun, Jimmy and Brandt, Jessica and Lopez Salas, Nieves and Lai, Feili and Li, Qiuye and Liu, Tianxi and Amal, Rose and Lu, Xunyu and Antonietti, Markus}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, number = {{37}}, publisher = {{Wiley}}, title = {{{Constructing Interfacial Boron‐Nitrogen Moieties in Turbostratic Carbon for Electrochemical Hydrogen Peroxide Production}}}, doi = {{10.1002/anie.202206915}}, volume = {{61}}, year = {{2022}}, } @article{62677, abstract = {{AbstractThe influence of structural modifications on the catalytic activity of carbon materials is poorly understood. A collection of carbonaceous materials with different pore networks and high nitrogen content was characterized and used to catalyze four reactions to deduce structure–activity relationships. The CO2 cycloaddition and Knoevenagel reaction depend on Lewis basic sites (electron‐rich nitrogen species). The absence of large conjugated carbon domains resulting from the introduction of large amounts of nitrogen in the carbon network is responsible for poor redox activity, as observed through the catalytic reduction of nitrobenzene with hydrazine and the catalytic oxidation of 3,3′,5,5′‐tetramethylbenzidine using hydroperoxide. The material with the highest activity towards Lewis acid catalysis (in the hydrolysis of (dimethoxymethyl)benzene to benzaldehyde) is the most effective for small molecule activation and presents the highest concentration of electron‐poor nitrogen species.}}, author = {{Lepre, Enrico and Rat, Sylvain and Cavedon, Cristian and Seeberger, Peter H. and Pieber, Bartholomäus and Antonietti, Markus and Lopez Salas, Nieves}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, number = {{2}}, publisher = {{Wiley}}, title = {{{Catalytic Properties of High Nitrogen Content Carbonaceous Materials}}}, doi = {{10.1002/anie.202211663}}, volume = {{62}}, year = {{2022}}, } @article{33653, author = {{Gurinov, Andrei and Sieland, Benedikt and Kuzhelev, Andrey and Elgabarty, Hossam and Kühne, Thomas and Prisner, Thomas and Paradies, Jan and Baldus, Marc and Ivanov, Konstantin L. and Pylaeva, Svetlana}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, number = {{28}}, pages = {{15371--15375}}, publisher = {{Wiley}}, title = {{{Mixed‐Valence Compounds as Polarizing Agents for Overhauser Dynamic Nuclear Polarization in Solids}}}, doi = {{10.1002/anie.202103215}}, volume = {{60}}, year = {{2021}}, } @article{47965, abstract = {{Exceptionally electron-rich, nearly trigonal-planar tricyanidometalate anions [Fe(CN)3]7− and [Ru(CN)3]7− were stabilized in LiSr3[Fe(CN)3] and AE3.5[M(CN)3] (AE=Sr, Ba; M=Fe, Ru). They are the first examples of group 8 elements with the oxidation state of −IV. Microcrystalline powders were obtained by a solid-state route, single crystals from alkali metal flux. While LiSr3[Fe(CN)3] crystallizes in P63/m, the polar space group P63 with three-fold cell volume for AE3.5[M(CN)3] is confirmed by second harmonic generation. X-ray diffraction, IR and Raman spectroscopy reveal longer C−N distances (124–128 pm) and much lower stretching frequencies (1484–1634 cm−1) than in classical cyanidometalates. Weak C−N bonds in combination with strong M−C π-bonding is a scheme also known for carbonylmetalates. Instead of the formal notation [Fe−IV(CN−)3]7−, quantum chemical calculations reveal non-innocent intermediate-valent CN1.67− ligands and a closed-shell d10 configuration for Fe, that is, Fe2−.}}, author = {{Jach, Franziska and Wagner, Frank R. and Amber, Zeeshan H. and Rüsing, Michael and Hunger, Jens and Prots, Yurii and Kaiser, Martin and Bobnar, Matej and Jesche, Anton and Eng, Lukas M. and Ruck, Michael and Höhn, Peter}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, number = {{29}}, pages = {{15879--15885}}, publisher = {{Wiley}}, title = {{{Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non‐Innocent Cyanido Ligands}}}, doi = {{10.1002/anie.202103268}}, volume = {{60}}, year = {{2021}}, }