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The Interplay of Single Ion Anisotropy and Magnetic 3 d-4 f Interactions in VIII2LnIII2 Butterfly Complexes VIII2LnIII2蝴蝶配合物中单离子各向异性与磁性3d - 4f相互作用的相互作用

ChemistryEurope Pub Date : 2025-04-11 DOI: 10.1002/ceur.202500011

Jan Arneth, Dr. Xian-Feng Li, Dr. Jonas Braun, Dr. Sagar Paul, Dr. Michael Schulze, Dr. Christopher E. Anson, Prof. Dr. Wolfgang Wernsdorfer, Prof. Dr. Annie K. Powell, Prof. Dr. Rüdiger Klingeler

{"title":"The Interplay of Single Ion Anisotropy and Magnetic 3 d-4 f Interactions in VIII2LnIII2 Butterfly Complexes","authors":"Jan Arneth, Dr. Xian-Feng Li, Dr. Jonas Braun, Dr. Sagar Paul, Dr. Michael Schulze, Dr. Christopher E. Anson, Prof. Dr. Wolfgang Wernsdorfer, Prof. Dr. Annie K. Powell, Prof. Dr. Rüdiger Klingeler","doi":"10.1002/ceur.202500011","DOIUrl":"https://doi.org/10.1002/ceur.202500011","url":null,"abstract":"Within the framework of 3d–4f molecular magnets, the most thoroughly investigated architecture is that of butterfly-shaped coordination clusters as it provides an ideal testbed to study fundamental magnetic interactions. Here, we report the synthesis and characterisation of a series of isostructural VIII2LnIII2 butterfly complexes, where Ln=Y (1Y), Tb (2Tb), Dy (3Dy), Ho (4Ho), Er (5Er), Tm (6Tm), Yb (7Yb), which extends the previous study on isostructural butterflies with CrIII, MnIII and FeIII. In zero external field, compounds 2Tb, 3Dy and 4Ho show clear maxima in the out-of-phase component of the ac susceptibility whereas small magnetic fields are needed to suppress quantum tunnelling in 6Tm. Combined high-field electron paramagnetic resonance spectroscopy and magnetisation measurements unambiguously reveal an easy-plane anisotropy of the VIII ion and antiferromagnetic Ising-like 3d–4f exchange couplings. The strength of J3d-4f is shown to decrease upon variation of the 4 f ion from Tb to Ho, while increasing antiferromagnetic interaction can be observed from Ho to Tm. The exact inverse chemical trend is found for the relative angle between the 3d and 4 f main anisotropy axes, which highlights the important role of the lanthanide 4 f electron distribution anisotropy for 3d–4f exchange.","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500011","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949894","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Self-Assembly of Silver Nanoclusters by Cooperative Acetylene Bonding with Mutual Pyridyl Coordination 协同乙炔键与相互吡啶配位的银纳米团簇自组装

ChemistryEurope Pub Date : 2025-04-10 DOI: 10.1002/ceur.202500069

Tasuki Tsurumi, Takahiro Nakagawa, Takashi Kikuchi, Kiyohiro Adachi, Hironobu Hayashi, Atsuro Takai, Takuma Kaneko, Tomoya Uruga, Daisuke Hashizume, Yosuke Nakamura, Makoto Fujita, Yuya Domoto

{"title":"Self-Assembly of Silver Nanoclusters by Cooperative Acetylene Bonding with Mutual Pyridyl Coordination","authors":"Tasuki Tsurumi, Takahiro Nakagawa, Takashi Kikuchi, Kiyohiro Adachi, Hironobu Hayashi, Atsuro Takai, Takuma Kaneko, Tomoya Uruga, Daisuke Hashizume, Yosuke Nakamura, Makoto Fujita, Yuya Domoto","doi":"10.1002/ceur.202500069","DOIUrl":"https://doi.org/10.1002/ceur.202500069","url":null,"abstract":"The controlled supramolecular alignment of atomically precise metal nanoclusters is a promising method to unlock unprecedented properties and advanced functions beyond those of the individual monomeric nanoclusters. Conventional protocols for the construction of such assemblies require the use of two or more types of ligands for protecting and interconnecting the nanoclusters, respectively. Herein, a strategy is demonstrated for the hierarchical self-assembly of an alkyne-protected silver nanocluster into a 3D network in the crystalline lattice based on cooperative silver···acetylene coordination and silver···pyridyl coordination by a bifunctional ligand with a simple design. The bent ligand L produces a Cl@Ag14L12 monomer with a helical conformation resembling that of organic tripodal ligands, which assembles into a 3D network as evident from a single-crystal X-ray diffraction analysis. The monomeric and network structures are further characterized using grazing-incidence small-angle X-ray scattering, atomic force microscopy, X-ray photoelectron spectroscopy, and X-ray absorption fine structure, in addition to photoluminescence with a microsecond lifetime in the solid state, exhibiting the success of the strategy toward the design of self-assembled 3D supramolecular arrangements of atomically precise metal nanoclusters using a single, simple ligand.","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500069","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635000","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Multiple Atropo Selectivity by κ2-N,O-Oxazoline Urea Ligands in Cobaltaelectro-Catalyzed C─H Activations: Decoding Selectivity with Data Science Integration κ2-N， o-恶唑啉脲配体在钴电催化C─H活化中的多重阿托普选择性：解码选择性与数据科学集成

ChemistryEurope Pub Date : 2025-04-08 DOI: 10.1002/ceur.202500071

Philipp Boos, Neeraj Kumar Pandit, Suman Dana, Tristan von Münchow, Airu Hashidoko, Laura Haberstock, Regine Herbst-Irmer, Dietmar Stalke, Lutz Ackermann

{"title":"Multiple Atropo Selectivity by κ2-N,O-Oxazoline Urea Ligands in Cobaltaelectro-Catalyzed C─H Activations: Decoding Selectivity with Data Science Integration","authors":"Philipp Boos, Neeraj Kumar Pandit, Suman Dana, Tristan von Münchow, Airu Hashidoko, Laura Haberstock, Regine Herbst-Irmer, Dietmar Stalke, Lutz Ackermann","doi":"10.1002/ceur.202500071","DOIUrl":"https://doi.org/10.1002/ceur.202500071","url":null,"abstract":"Enantioselective catalysis is one of the most prominent strategies in organic synthesis to access chiral bioactive compounds and advanced organic materials. Particularly, the development of chiral ligands has significantly advanced the efficiency and selectivity of transition metal-catalyzed enantioselective transformations. Over recent decades, numerous chiral ligand classes with distinct geometrical and electronic properties have been established. Despite these advances, the demand for novel, tunable, and highly effective chiral ligands persists, driven by the need for structurally diverse chiral molecules and the pursuit of greener, more sustainable catalytic processes. Herein, a novel class of chiral oxazoline ureas is introduced and their potential as κ2-N,O-preligands in enantioselective transition metal catalysis is demonstrated. The chiral oxazoline urea ligands are featurized and compared with amide and enol derivatives using the physical organic descriptors. A multivariate linear regression model is constructed to quantitatively describe the effect of the quinoline fragment from the substrate and the ligand on enantioselectivity. Moreover, the model is effectively applied to atropo-enantioselective cobaltaelectro-catalyzed C─H annulations of 1-alkynyl indoles.","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500071","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949805","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Fluorescent Probe for δ-Cyclodextrin Enables Guest Encapsulation Studies via an Indicator Displacement Assay δ-环糊精荧光探针使客包封研究通过指示剂置换试验

ChemistryEurope Pub Date : 2025-04-03 DOI: 10.1002/ceur.202500029

Mads G. Rasmussen, Giorgia Masciotta, Kasper H. Hansen, Andreas Erichsen, Gustav Schjær Hummelshøj, Panagiota Kalomoiri, Sebastian Meier, Sophie R. Beeren

{"title":"Fluorescent Probe for δ-Cyclodextrin Enables Guest Encapsulation Studies via an Indicator Displacement Assay","authors":"Mads G. Rasmussen, Giorgia Masciotta, Kasper H. Hansen, Andreas Erichsen, Gustav Schjær Hummelshøj, Panagiota Kalomoiri, Sebastian Meier, Sophie R. Beeren","doi":"10.1002/ceur.202500029","DOIUrl":"https://doi.org/10.1002/ceur.202500029","url":null,"abstract":"Molecular containers are important tools to enhance the solubility and stability of bioactive compounds in water, and new macrocyclic scaffolds will expand the range of guests that can be encapsulated. α-, β-, and γ-Cyclodextrin (CD), and derivatives thereof, are widely utilized for the complexation of active ingredients in product formulation, but large-ring CDs, formed from more than eight glucose units, have been little explored due to a lack of availability. The recent development of a multi-gram synthesis of δ-CD (formed from nine glucopyranose units) means that this larger CD could now become a viable candidate for encapsulation of previously untargetable guests. Herein, it is reported that a bolaamphiphile with pyranine headgroups can act as a fluorescent probe for sensing of δ-CD. Binding studies using fluorescence and NMR spectroscopy, as well as molecular dynamics simulations, reveal that partial unfolding of the bolaamphiphile upon binding to δ-CD leads to fluorescence enhancement. It is showcased how this fluorescent probe can be implemented in an indicator displacement assay to detect host–guest interactions with δ-CD. This proof-of-principle study paves the way forward toward high- throughput optical assays to screen libraries of bioactive guests and realize the potential of δ-CD as a newly accessible molecular container.","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500029","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949999","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanochemical Synthesis of Pillar[5]arene-based [c2]Daisy Chain Rotaxanes 柱状[5]芳烃基[c2]菊花链轮烷的机械化学合成

ChemistryEurope Pub Date : 2025-04-03 DOI: 10.1002/ceur.202500002

Dr. Boram Park, Dr. Iwona Nierengarten, Dr. Jean-François Nierengarten

引用次数: 0

pH-Controlled Gliding Motions in Pillar[5]arene-Containing Molecular Shuttles 柱状[5]含芳烃分子梭的ph控制滑动运动

ChemistryEurope Pub Date : 2025-04-02 DOI: 10.1002/ceur.202400115

Nihed Becharguia, Iwona Nierengarten, Alix Sournia-Saquet, Emeric Wasielewski, Rym Abidi, Béatrice Delavaux-Nicot, Jean-François Nierengarten

引用次数: 0

Label-Free Photonic Biosensors: Key Technologies for Precision Diagnostics 无标签光子生物传感器：精密诊断的关键技术

ChemistryEurope Pub Date : 2025-03-30 DOI: 10.1002/ceur.202400106

Maria Soler, Laura M. Lechuga

{"title":"Label-Free Photonic Biosensors: Key Technologies for Precision Diagnostics","authors":"Maria Soler, Laura M. Lechuga","doi":"10.1002/ceur.202400106","DOIUrl":"https://doi.org/10.1002/ceur.202400106","url":null,"abstract":"With the rise of multidrug-resistant pathogens, emerging zoonotic viruses, and the increasing prevalence of cancer, the modernization of clinical diagnostics has become a critical priority. Label-free optical biosensors, including those based on plasmonics and silicon photonic technologies, offer promising solutions for highly sensitive molecular analysis, rapid assay times, and decentralized operation. However, important challenges must be addressed for their successful clinical implementation, including the miniaturization and integration in compact, automated devices and the direct analysis of complex human specimens, like blood. In this context, an overview of recent advancements and future perspectives in photonic biosensors are provided for clinical diagnostics. The critical limitations of these technologies are examined, and specific research objectives that need to be met to fully leverage the potential of photonic biosensors and accelerate their adoption in the clinical practice are proposed. Finally, the most innovative biosensor designs and methodologies are highlighted, along with their prospects for contributing to precision diagnosis and personalized medicine.","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400106","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

AzUlene-Fused Polycyclic Aromatic Hydrocarbons: Synthesis, Structural, Optical, and Electrochemical Properties of Azuleno[2,1-a]phenalenones Azuleno[2,1-a]苯烯酮的合成、结构、光学和电化学性质

ChemistryEurope Pub Date : 2025-03-27 DOI: 10.1002/ceur.202500039

Taku Shoji, Naoko Sakata, Ryunosuke Ishikawa, Shigeki Mori, Tetsuo Okujima, Ryuta Sekiguchi, Shunji Ito

引用次数: 0

Chemoselective or Regioselective? 化学选择性还是区域选择性？

ChemistryEurope Pub Date : 2025-03-27 DOI: 10.1002/ceur.202500045

Andrej Kolarovič, Pavol Jakubec

引用次数: 0

Mechanochemical Enantiospecific Syntheses of Sulfonimidate Esters and Sulfonimidamides by Various S(VI) Exchange Reactions 各种S（VI）交换反应的机械化学对映性合成磺酰咪酯和磺酰咪酰胺

ChemistryEurope Pub Date : 2025-03-27 DOI: 10.1002/ceur.202500006

Shashank Tripathi, Sidharam P. Pujari, Manoah Romkes, Fedor M. Miloserdov, Hongwei Zhou, Han Zuilhof

引用次数: 0