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Spin-Crossover Modulated Luminescence in Materials and Molecular Complexes 材料和分子配合物中的自旋交叉调制发光
IF 1.8 4区 化学
Helvetica Chimica Acta Pub Date : 2026-01-06 DOI: 10.1002/hlca.202500180
Charlotte Egger, Claude Piguet
{"title":"Spin-Crossover Modulated Luminescence in Materials and Molecular Complexes","authors":"Charlotte Egger,&nbsp;Claude Piguet","doi":"10.1002/hlca.202500180","DOIUrl":"https://doi.org/10.1002/hlca.202500180","url":null,"abstract":"<p>The abrupt reorganization of the electronic configuration of spin-crossover (SCO) compounds upon the transition from the low-spin (LS) to the high-spin (HS) state leads to significant changes in their structural, optical, and magnetic properties. As spin-transitions can be triggered by a variety of external stimuli such as variations in temperature, pressure, or through light irradiation, these systems have attracted considerable attention for the design of multifunctional and stimuli-responsive molecular materials. In this context, the synergistic coupling of SCO and luminescent properties holds great promise for the development of molecular spintronic devices capable of correlating the luminescence with an external perturbation, or of probing the magnetic state of the metal center through variations in emission intensity. This contribution provides a comprehensive overview of the field of luminescent SCO materials, with particular emphasis on systems that exhibit a genuine interplay between the two properties, both in materials and at the molecular level.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500180","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146223942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A General Platform for the Light-Enabled Generation of α-Fluoro Radicals Leveraging Simple Additives 利用简单添加剂生成α-氟自由基的通用平台
IF 1.8 4区 化学
Helvetica Chimica Acta Pub Date : 2025-12-27 DOI: 10.1002/hlca.202500214
Jonas Klagge, Maria Mazhuga, John J. Molloy
{"title":"A General Platform for the Light-Enabled Generation of α-Fluoro Radicals Leveraging Simple Additives","authors":"Jonas Klagge,&nbsp;Maria Mazhuga,&nbsp;John J. Molloy","doi":"10.1002/hlca.202500214","DOIUrl":"https://doi.org/10.1002/hlca.202500214","url":null,"abstract":"<p>The strategic generation of α-fluoro radicals underpins powerful routes to fluorine-rich architectures of high value in molecular design. Here, we disclose an operationally simple, catalyst-free method for the photochemical activation of α-halo fluorinated precursors using visible light and two inexpensive additives, sodium iodide and 2,6-lutidine. This mild protocol enables in-situ halide exchange and subsequent homolytic C–I bond scission to generate α-fluoro radicals under ambient conditions. The generality of the platform is demonstrated across esters, sulphones, and nitriles, facilitating intermolecular coupling with alkenes, heteroarenes, and propellanes to access diverse fluorinated scaffolds. Mechanistic studies support the formation of a weak electron donor–acceptor complex that mediates bond activation, while the benign conditions permit merger with energy transfer catalysis for stereodivergent product formation.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500214","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146224353","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Noninvasive Disease Diagnostics: The Swiss Contribution Highlights to Breath Analysis Research 无创疾病诊断：瑞士对呼吸分析研究的贡献亮点
IF 1.8 4区 化学
Helvetica Chimica Acta Pub Date : 2025-12-23 DOI: 10.1002/hlca.202500193
Stefan James Swift, Kseniya Dryahina, Patrik Španěl, Flora Kontopidou, Christos Kokkotis, Renato Zenobi, Stamatios Giannoukos
{"title":"Noninvasive Disease Diagnostics: The Swiss Contribution Highlights to Breath Analysis Research","authors":"Stefan James Swift,&nbsp;Kseniya Dryahina,&nbsp;Patrik Španěl,&nbsp;Flora Kontopidou,&nbsp;Christos Kokkotis,&nbsp;Renato Zenobi,&nbsp;Stamatios Giannoukos","doi":"10.1002/hlca.202500193","DOIUrl":"https://doi.org/10.1002/hlca.202500193","url":null,"abstract":"<p>To celebrate the 125th anniversary of the Swiss Chemical Society, we present a review and perspective to highlight the recent research in breath analysis that has been conducted in Switzerland, with a particular focus on secondary electrospray ionization mass spectrometry (SESI-HR-MS). We focus on breath analysis research from 2019, the publication year of the last major review. We highlight where improvements are needed in experimental and clinical protocols and outline the current gaps in the field, to support the implementation of breath analysis into the clinical domain.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500193","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320910","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Exploring Remote C─H Bond Arylation: Transition Metal Catalysis Without “End-On Template” 探索远程C─H键芳基化：无端上模板的过渡金属催化
IF 1.8 4区 化学
Helvetica Chimica Acta Pub Date : 2025-12-19 DOI: 10.1002/hlca.202500208
Biprajit Paul, Indranil Chatterjee
{"title":"Exploring Remote C─H Bond Arylation: Transition Metal Catalysis Without “End-On Template”","authors":"Biprajit Paul,&nbsp;Indranil Chatterjee","doi":"10.1002/hlca.202500208","DOIUrl":"https://doi.org/10.1002/hlca.202500208","url":null,"abstract":"<div>\u0000 \u0000 <p>C─H bond functionalization has appeared as one of the most efficient tools for building complex molecular scaffolds. Despite growing interest in remote C─H bond functionalization, achieving the distal site selectivity is highly challenging. Traditional <i>“end-on template”</i> based methods usually require additional steps for installing and removing long directing templates, and often rely on expensive transition metals, which makes the process less sustainable. In this essay, an alternative concept known as <i>“complementary catalysis”</i> is discussed to achieve remote C─H arylation without the use of large templates. This approach requires a small directing group to control regioselectivity under mild conditions without any externally added ligands or activators. Most importantly, it paves a more sustainable route by improving the atom and step economy.</p>\u0000 </div>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146224265","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Methylene-Bridged Calixarene Polyhedra: An Elusive Class of Symmetric Molecular Architectures 亚甲基桥接杯芳烃多面体：一类难以捉摸的对称分子结构
IF 1.8 4区 化学
Helvetica Chimica Acta Pub Date : 2025-12-16 DOI: 10.1002/hlca.202500177
Aleksandr Kharchenko, Ivan Cornu, Bernd Goldfuss, Konrad Tiefenbacher
{"title":"Methylene-Bridged Calixarene Polyhedra: An Elusive Class of Symmetric Molecular Architectures","authors":"Aleksandr Kharchenko,&nbsp;Ivan Cornu,&nbsp;Bernd Goldfuss,&nbsp;Konrad Tiefenbacher","doi":"10.1002/hlca.202500177","DOIUrl":"https://doi.org/10.1002/hlca.202500177","url":null,"abstract":"<p>This perspective highlights a distinctive class of symmetric molecular architectures, methylene-bridged calixarene polyhedral, that, despite long-standing theoretical interest, have not yet been synthesized. It consolidates all previously proposed members of this family, introduces a new representative, and assesses their synthetic feasibility through computational strain analyses. Five polyhedra were examined: methanospherophane, Cram's prototype carcerand, two augmented prismatic dimers, and the newly postulated calix[5]arene-based icosidodecahedron. Homodesmotic hydrogenolysis reactions were employed to estimate strain energies, complemented by angular deviation analysis from ideal collinearity (180°). Among all candidates, the methanospherophane emerged as the only nearly strain-free structure, while Cram's carcerand and the icosidodecahedron exhibited significant strain. The prismatic dimers showed intermediate stability. Methanospherophane thus emerges as the leading candidate for the first successful synthesis, potentially opening the door to this fascinating class of methylene-bridged calixarene polyhedra.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500177","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146217121","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
C2-Alkenylation of Indoles via Reverse-Allylation-Isomerization Cascade 反烯丙化-异构级联反应中吲哚的c2 -烯基化反应
IF 1.8 4区 化学
Helvetica Chimica Acta Pub Date : 2025-12-15 DOI: 10.1002/hlca.202500181
Soumitra Majee, Sangram Samanta, Dinabandhu Samanta, Modhu Sudan Maji
{"title":"C2-Alkenylation of Indoles via Reverse-Allylation-Isomerization Cascade","authors":"Soumitra Majee,&nbsp;Sangram Samanta,&nbsp;Dinabandhu Samanta,&nbsp;Modhu Sudan Maji","doi":"10.1002/hlca.202500181","DOIUrl":"https://doi.org/10.1002/hlca.202500181","url":null,"abstract":"<div>\u0000 \u0000 <p>The directing group free alkenylation of indoles is underdeveloped and a highly desirable transformation in the field of π-excessive heterocycle chemistry. In this study to access C2-alkenylindoles, 3-chloroindoles were utilized as C2-indolyl electrophiles toward allyl boronic acid nucleophiles. This approach provides access to NH-free C2-alkenylindoles bearing no substitution at their C3-position. The reversed-allylated products underwent in situ isomerization under the influence of Lewis acidic allyl boronic acid, eventually delivering the desired 2-alkenyl indoles. A range of electronically different indoles took part in this reaction, providing products in good yields, and diastereoselectivities vary depending on the steric nature of allyl moieties. Synthesis of carbazole-based alkaloids hyellazole and 6-chlorohyellazole demonstrated the synthetic utility of this one-pot cascade protocol.</p>\u0000 </div>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147269035","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
The Versatility of Imidazole and Imidazolium Scaffolds in Sustainable Chemistry and Energy Conversion 咪唑和咪唑支架在可持续化学和能量转化中的多功能性
IF 1.8 4区 化学
Helvetica Chimica Acta Pub Date : 2025-12-12 DOI: 10.1002/hlca.202500188
Lianghui Li, Shun Tian, Enze Xu, Zhaofu Fei, Paul J. Dyson
{"title":"The Versatility of Imidazole and Imidazolium Scaffolds in Sustainable Chemistry and Energy Conversion","authors":"Lianghui Li,&nbsp;Shun Tian,&nbsp;Enze Xu,&nbsp;Zhaofu Fei,&nbsp;Paul J. Dyson","doi":"10.1002/hlca.202500188","DOIUrl":"https://doi.org/10.1002/hlca.202500188","url":null,"abstract":"<p>Imidazole is a versatile heteroaromatic ring whose properties can be systematically tuned through substitution. N-alkylation or N-arylation yields imidazolium cations, which are frequently low-melting and are then described as ionic liquids (ILs), and as precursors to N-heterocyclic carbene (NHC) ligands. Substitution at the 4- and 5-positions modulates the electronic and steric profiles of the five-membered ring. Imidazole and imidazolium derivatives not only serve as solvents, catalysts, and cocatalysts in the reduction of CO<sub>2</sub>, but also act as electrolytes in dye-sensitized solar cells (DSSCs) and as hole-transport materials and multifunctional additives in perovskite solar cells (PSCs). Hence, the combination of imidazole/imidazolium-based materials with versatile structures can bridge molecular design with high-performance catalysis and photovoltaics. This mini-review aims to survey imidazole/imidazolium-scaffold structures and their applications in sustainable chemistry and energy conversion, providing a perspective on the structure–function relationships and future directions.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500188","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146216921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Sulfonamide-Derived N,N,N-Ligand Enabled Copper-Catalyzed Radical 1,2-Trichloromethylthioesterification of Styrenes 磺胺衍生N，N，N配体使能铜催化苯乙烯自由基1,2-三氯甲基硫代酯化反应
IF 1.8 4区 化学
Helvetica Chimica Acta Pub Date : 2025-12-12 DOI: 10.1002/hlca.202500184
Zhi-Chao Chen, Fu Liu, Derong Cao, Peng-Fei Wang, Yu Tian, Xin-Yuan Liu
{"title":"Sulfonamide-Derived N,N,N-Ligand Enabled Copper-Catalyzed Radical 1,2-Trichloromethylthioesterification of Styrenes","authors":"Zhi-Chao Chen,&nbsp;Fu Liu,&nbsp;Derong Cao,&nbsp;Peng-Fei Wang,&nbsp;Yu Tian,&nbsp;Xin-Yuan Liu","doi":"10.1002/hlca.202500184","DOIUrl":"https://doi.org/10.1002/hlca.202500184","url":null,"abstract":"<div>\u0000 \u0000 <p>The copper-catalyzed radical difunctionalization of alkenes using readily accessible carbon tetrachloride (CCl<sub>4</sub>) and potassium benzothioate offers an attractive approach for thioester synthesis. Major challenges stem from the weak reducing capacity of copper catalysts in their ground state and the facile atom transfer radical addition between CCl<sub>4</sub> and alkenes. In this work, we describe an efficient radical 1,2-trichloromethylthioesterification of styrenes conducted under mild thermal conditions. The effectiveness of this approach depends on the application of an anionic sulfonamide-derived N,N,N-ligand, which not only boosts the reducing capability of the copper catalyst to initiate the reaction but also promotes the formation of C(sp<sup>3</sup>)–S bonds. This method exhibits a broad substrate scope, thus serving as a valuable complement to existing 1,2-carbothiolation of alkenes. Mechanistic investigations confirm that a radical mechanism is operative.</p>\u0000 </div>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 2","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146680449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis of Biphenanthrene Natural Products by Atroposelective Aromatic Ring-Opening Metathesis 芳香开环复分解法合成二菲天然产物
IF 1.8 4区 化学
Helvetica Chimica Acta Pub Date : 2025-12-08 DOI: 10.1002/hlca.202500210
Valeriia Hutskalova, Christof Sparr
{"title":"Synthesis of Biphenanthrene Natural Products by Atroposelective Aromatic Ring-Opening Metathesis","authors":"Valeriia Hutskalova,&nbsp;Christof Sparr","doi":"10.1002/hlca.202500210","DOIUrl":"https://doi.org/10.1002/hlca.202500210","url":null,"abstract":"<p>With the unique ability to cleave and form an extensive range of carbon–carbon double and triple bonds, alkene and alkyne metathesis advanced to a preferred strategy for the synthesis of natural products. Furthermore, metathesis is ideally suited for cascade reactions and, if well-defined chiral catalysts are employed, even for enantioselective transformations. However, while alkene and alkyne metathesis are frequently employed in the preparation of naturally occurring structures, the ring-opening metathesis of arenes, which are prevalent in natural compounds, is not yet established as avenue for natural product total synthesis. Herein, we now describe that aromatic ring-opening metathesis (ArROM) allows particularly short and efficient total syntheses of aromatic natural products. Moreover, by atroposelective ArROM, synthetic access to naturally occurring biphenanthrene atropisomers was possible with outstanding stereoselectivity, allowing to corroborate unusual differences in their configurational stability under ambient light.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 1","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500210","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Isomerization of α-Pinene Oxide to Trans-Pinocarveol α-蒎烯氧化物异构化制备反式蒎醇
IF 1.8 4区 化学
Helvetica Chimica Acta Pub Date : 2025-12-08 DOI: 10.1002/hlca.202500187
Emanuel Studer, Johanna Oortmann, Ryan Gilmour
{"title":"Isomerization of α-Pinene Oxide to Trans-Pinocarveol","authors":"Emanuel Studer,&nbsp;Johanna Oortmann,&nbsp;Ryan Gilmour","doi":"10.1002/hlca.202500187","DOIUrl":"https://doi.org/10.1002/hlca.202500187","url":null,"abstract":"<p>In addition to being a natural fragrance and EU/WHO-approved food additive, the bicyclic monoterpene <i>trans</i>-pinocarveol (TPC) is a versatile chiral building block for the generation of societally important small molecules. Selective oxidation strategies that leverage <i>α</i>-pinene constitute the most direct and sustainable routes to access this target, where they remain in the vanguard of contemporary approaches to generate molecular complexity from this chiral pool resource. However, the subsequent isomerization of <i>α</i>-pinene oxide (APO) to TPC is complicated by competing 1,2-alkyl shifts leading to inevitable for action of various monocyclic products. Motivated by this challenge, an operationally simple protocol to enable the efficient isomerization of APO to TPC is disclosed that leverages inexpensive pyridinium halides as catalysts. This enabling strategy can be performed on a decagram scale, and catalyst recycling is demonstrated through the deployment of HBr-treated commercial 4-polyvinylpyridine.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 1","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500187","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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