Helvetica Chimica Acta最新文献_第3页

Isomer Engineering of Phenazine and Tetraphenylethylene Derivatives for Enhanced Fluorescence in both Solid and Aggregation States 非那嗪和四苯基乙烯衍生物在固体和聚集状态下增强荧光的异构体工程

IF 1.9 4区化学

Helvetica Chimica Acta Pub Date : 2026-07-18 Epub Date: 2026-07-02 DOI: 10.1002/hlca.70086

Jiaqin He, Yina Gu, Wenxiu Guo, Xun Chen, Junliang Liu, Genlin Wang, Shiyuan Zhou, Peiyang Gu

{"title":"Isomer Engineering of Phenazine and Tetraphenylethylene Derivatives for Enhanced Fluorescence in both Solid and Aggregation States","authors":"Jiaqin He, Yina Gu, Wenxiu Guo, Xun Chen, Junliang Liu, Genlin Wang, Shiyuan Zhou, Peiyang Gu","doi":"10.1002/hlca.70086","DOIUrl":"https://doi.org/10.1002/hlca.70086","url":null,"abstract":"<div>\u0000 \u0000 Isomer engineering represents a strategy that preserves both the electron donor-acceptor connectivity and elemental composition of fluorescent molecules, while enables effective modulation of the electronic structure and holds potential for elucidating the influence of molecular architecture on fluorescence behavior. In this work, four new phenazine and tetraphenylethylene (TPE) derivatives were designed and synthesized through an isomer engineering strategy and a Suzuki-Miyaura coupling reaction. The TPE-based luminogens were introduced into the phenazine core at the 2,7- or 3,6-positions, resulting in the designation of the four compounds as 27TNE, 36TNE, 27TE, and 36TE, respectively. Among them, 27TNE and 36TNE exhibit characteristic aggregation-induced emission properties with high fluorescence quantum yields in the solid state (0.49 for 27TNE, 0.35 for 36TNE), whereas 27TE and 36TE show dual-state emission (DSE) with moderate fluorescence in both solution (0.74 for 27TE, and 0.64 for 36TE in dimethylformamide (DMF)) and solid states. The density functional theory calculations reveal the influence of different isomerization and central cores on the fluorescence behavior of these compounds.\u0000 </div>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 7","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148532649","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

Mechanosynthesis of Metal-Free Molecular Perovskites 无金属分子钙钛矿的机械合成

IF 1.9 4区化学

Helvetica Chimica Acta Pub Date : 2026-07-18 Epub Date: 2026-06-17 DOI: 10.1002/hlca.202500237

Gianluca Bravetti, Aki Frankberg, Mahsa Shahsavan, Paul Zimmermann, Benjamin M. Gallant, Oleg Konovalov, Mohammad Reza Golobostanfard, Alexander Hinderhofer, Frank Schreiber, Dominik J. Kubicki, Jovana V. Milić

{"title":"Mechanosynthesis of Metal-Free Molecular Perovskites","authors":"Gianluca Bravetti, Aki Frankberg, Mahsa Shahsavan, Paul Zimmermann, Benjamin M. Gallant, Oleg Konovalov, Mohammad Reza Golobostanfard, Alexander Hinderhofer, Frank Schreiber, Dominik J. Kubicki, Jovana V. Milić","doi":"10.1002/hlca.202500237","DOIUrl":"https://doi.org/10.1002/hlca.202500237","url":null,"abstract":"Metal-free halide perovskites have recently emerged as promising candidates for optoelectronic applications. However, their synthesis has largely depended on water-based single-crystal growth that limits material diversity, scalability, and practical implementation. Here, we present a mechanochemical route to synthesize N,N-diazabicyclo[2.2.2]octonium (H-DABCO)-based halide perovskites from the (DABCO)(NH4)X3 (X = I, Br) compositions. The structural properties were confirmed by X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy. Thin films were prepared from mechanosynthetic powders by spin-coating and characterized by in-situ grazing incidence wide-angle scattering measurements, as well as by UV–vis absorption and steady-state photoluminescence spectroscopy. This mechanosynthetic strategy provides a scalable, environmentally friendly pathway to broaden the scope of metal-free perovskites and advance their potential in sustainable optoelectronic technologies.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 7","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500237","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148533753","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 Compact Circularly Polarized Luminescence Emitter–Chirality of a [2.2]-Paracyclophane Macrocycle 一个紧凑的圆极化发光体-[2.2]-副环环大环的手性

IF 1.9 4区化学

Helvetica Chimica Acta Pub Date : 2026-06-18 Epub Date: 2026-05-13 DOI: 10.1002/hlca.70078

Salome L. Heim, Adriano D'Addio, Olaf Fuhr, Dieter Fenske, Marcel Mayor

{"title":"A Compact Circularly Polarized Luminescence Emitter–Chirality of a [2.2]-Paracyclophane Macrocycle","authors":"Salome L. Heim, Adriano D'Addio, Olaf Fuhr, Dieter Fenske, Marcel Mayor","doi":"10.1002/hlca.70078","DOIUrl":"https://doi.org/10.1002/hlca.70078","url":null,"abstract":"Chiral organic molecules with pronounced chiroptical responses are of significant interest for applications ranging from bioimaging to optoelectronic devices. Herein, we report comprehensive chiroptical investigations of a compact [2.2]paracyclophane (PCP)- based macrocycle and its open precursor. While the synthesis of the structure was reported by the group of Michael Haley, chiroptical investigations were still missing. The rigid PCP core acts as a chiral template, inducing helical twisting within the conjugated diacetylene framework. Owing to its low atomic count, the compact macrocycle represents an attractive model system for combined experimental and computational studies, enabling fast DFT and TD-DFT calculations. The macrocycle and its open synthetic precursor were synthesized, structurally characterized, and, in both cases, enantiomers were separated on a chiral stationary phase HPLC. Absolute configurations were assigned through TD-DFT calculations. Optical measurements reveal enhanced conjugation and redshifted emission upon macrocyclization. Electric circular dichroism (ECD) spectra exhibit multiple intense cotton bands. Both macrocycle and open precursor display exceptionally high circularly polarized luminescence (CPL) dissymmetry factors, with glum around 10−2. Despite moderate CPL brightness, limited by the compounds’ quantum yields, these results demonstrate the strong chiral amplification imparted by the PCP. The presented scaffold provides a versatile platform for probing structure–property relationships in chiral conjugated macrocycles.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 6","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.70078","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148274897","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

Traceable Traceless Delivery Tags 可追踪的无痕交付标签

IF 1.9 4区化学

Helvetica Chimica Acta Pub Date : 2026-06-18 Epub Date: 2026-06-05 DOI: 10.1002/hlca.70081

Julia Moreno, Xudong Ren, Saidbakhrom Saidjalolov, Pierre Josso, Naomi Sakai, Stefan Matile

{"title":"Traceable Traceless Delivery Tags","authors":"Julia Moreno, Xudong Ren, Saidbakhrom Saidjalolov, Pierre Josso, Naomi Sakai, Stefan Matile","doi":"10.1002/hlca.70081","DOIUrl":"https://doi.org/10.1002/hlca.70081","url":null,"abstract":"This study elaborates on traceless tags for the thiol-mediated uptake (TMU) of amine-containing substrates of interest (SOIs). Traceless tags typically contain linkers that can be enzymatically cleaved to trigger the release of SOIs in their native form. To trace SOI release inside cells, the dual function of asparagusic acid (AspA) derivatives to enable TMU and to track the Golgi apparatus is explored. We tested two of the most popular cleavable linkers based on esterases and quinone reductases. Conjugated to AspA through alkyloxycarbonyloxymethyl (AOCOM) linkers, fluorescent SOIs entered cells by TMU and spread in the cytosol with or without a brief stop in the Golgi, depending on the structure. FRET probes further demonstrated that after arrival in the Golgi, SOIs are released from AspA into the lumen, where they linger before spreading to the cytosol and beyond. Quinone-based trimethyl locks (TML) are also compatible with TMU, but reductive cleavage after TMU appears to be slower in the Golgi. These results validate AOCOM and TML linkers for constructing traceless TMU tags for amine-containing SOIs and introduce AspA probes as dynamic-covalent chemistry tools to trace traceless tags inside cells and to track Golgi lumen and Golgi membranes simultaneously with separately visualizable fluorescent probes.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 6","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.70081","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148274854","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

Mechanophores for Mechano-Imaging in Polymeric Materials 高分子材料机械成像的机械基团

IF 1.9 4区化学

Helvetica Chimica Acta Pub Date : 2026-06-18 Epub Date: 2026-06-05 DOI: 10.1002/hlca.70080

Jess M. Clough

{"title":"Mechanophores for Mechano-Imaging in Polymeric Materials","authors":"Jess M. Clough","doi":"10.1002/hlca.70080","DOIUrl":"https://doi.org/10.1002/hlca.70080","url":null,"abstract":"In many of their applications, polymeric materials are expected to withstand mechanical loads, yet the molecular-scale processes that govern how stress localizes, redistributes, and ultimately leads to damage remain difficult to probe directly. Mechanophore-based mechanochromic systems offer a powerful approach to address this challenge by converting mechanical input into optical signals detectable with spectroscopic and microscopic techniques. In this Perspective, we highlight recent progress in the use of mechanophores as probes for imaging mechanical processes in solid-state polymers. We discuss how mechanophore activation can reveal molecular damage, stress localization, and time-dependent deformation processes, and how emerging reversible and multiplexed, or multimodal systems extend mechano-imaging to lower stress regimes. Finally, we outline key challenges for the field, including the development of new mechanophore scaffolds for quantitative mechano-imaging and scalable reporter systems suitable for real materials and structural health monitoring. Together, these advances position mechanophore-based mechano-imaging as a promising framework for interrogating and ultimately controlling the distribution and dissipation of mechanical energy in polymeric materials.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 6","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.70080","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148274853","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

Synthesis and Structure of Alkali-Metal Naphthylamides Solvated by Biorenewable 2-Methyltetrahydrofuran 生物可再生2-甲基四氢呋喃溶剂化碱金属萘酰胺的合成与结构

IF 1.9 4区化学

Helvetica Chimica Acta Pub Date : 2026-06-18 Epub Date: 2026-06-05 DOI: 10.1002/hlca.70082

Sophia Belrhomari, Eva Hevia

{"title":"Synthesis and Structure of Alkali-Metal Naphthylamides Solvated by Biorenewable 2-Methyltetrahydrofuran","authors":"Sophia Belrhomari, Eva Hevia","doi":"10.1002/hlca.70082","DOIUrl":"https://doi.org/10.1002/hlca.70082","url":null,"abstract":"Advancing the synthetic and constitutional knowledge of alkali-metal amides, here we report the synthesis and structural authentication of a family of alkali-metal N-phenyl-1-naphthylamides (1Li, 1Na, and 1K) obtained from the deprotonation of the parent amine by an alkali-metal alkyl base in hexane and using biorenewable 2-methyltetrahydrofuran (2-MeTHF) as a Lewis donor. The aggregation and degree of donor-solvation of these complexes differ depending on the nature of the alkali-metal. Furthermore, the lithium N-phenyl-1-naphthylamide complex 1Li can undergo further metalation on the peri position of the naphthyl ring using either nBuLi or nBuNa as a base to give complexes 2LiLi, and 2LiNa, respectively. X-ray crystallographic studies established the molecular structures of these complexes in which both alkali-metals are chelated by a novel C,N-dianionic bidentate ligand. Quenching of 2LiLi, and 2LiNa with D2O provided further evidence supporting that the NH, C(peri)-H di-metalation has occurred.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 6","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.70082","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148274855","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

Micellar Suzuki–Miyaura Reaction With Xylose Acetal Cosolvents: A Life Cycle Assessment Approach 胶束Suzuki-Miyaura反应与木糖缩醛共溶剂：生命周期评价方法

IF 1.9 4区化学

Helvetica Chimica Acta Pub Date : 2026-06-18 Epub Date: 2026-05-13 DOI: 10.1002/hlca.70079

Arian Bajramaj, Lara Amini, Mylène Soudani, Justine Horner, Esaïe Reusser, Michael U. Luescher, Fabrice Gallou, Roger Marti

{"title":"Micellar Suzuki–Miyaura Reaction With Xylose Acetal Cosolvents: A Life Cycle Assessment Approach","authors":"Arian Bajramaj, Lara Amini, Mylène Soudani, Justine Horner, Esaïe Reusser, Michael U. Luescher, Fabrice Gallou, Roger Marti","doi":"10.1002/hlca.70079","DOIUrl":"https://doi.org/10.1002/hlca.70079","url":null,"abstract":"The use of green solvents is a key element in making chemical processes more sustainable. In this work, three biobased solvents, diformyl xylose (DFX), dipropyl xylose (DPX), and n-butyl tetrahydrofurfuryl ether (Solvinol), were tested as cosolvents in the Suzuki–Miyaura reaction using micellar catalysis in water (TPGS-750-M system). 2% DPX gave > 99% conversion and 86% yield, while 2% DFX reached 86% conversion and 82% yield. Solvinol required 15% loading to give similar results. DFX was easily removed in the aqueous phase upon work-up, while DPX and Solvinol were more difficult to remove due to their poor water solubility and high boiling points. These results demonstrate the potential of biomass-derived solvents as green alternatives to classical organic solvents. The overall environmental efficiency of the various processes was assessed via our internal methodology. Their efficiency at low loadings supports their use in more sustainable and environmentally friendly processes.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 6","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.70079","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148274898","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

Crystal Orientation Independent Strong TERS Response in Anisotropic ReS2 on Gold 金上各向异性ReS2中与晶体取向无关的强TERS响应

IF 1.9 4区化学

Helvetica Chimica Acta Pub Date : 2026-06-18 Epub Date: 2026-05-14 DOI: 10.1002/hlca.202500236

Pavel Valencia-Acuna, Chih-Feng Wang, Oliva M. Primera-Pedrozo, Andrey Krayev

{"title":"Crystal Orientation Independent Strong TERS Response in Anisotropic ReS2 on Gold","authors":"Pavel Valencia-Acuna, Chih-Feng Wang, Oliva M. Primera-Pedrozo, Andrey Krayev","doi":"10.1002/hlca.202500236","DOIUrl":"https://doi.org/10.1002/hlca.202500236","url":null,"abstract":"<div>\u0000 \u0000 Rhenium disulfide (ReS2) crystallizes in a distorted 1T′ lattice with triclinic symmetry arising from Re─Re dimerization, which produces in-plane anisotropic properties and a dense set of Raman-active modes with mixed atomic displacements. Prior conventional Raman microscopy studies in this material showed strong dependence of absolute and relative intensities of some Raman bands on the mutual orientation of the optical electric field and the in-plane crystalline axii. In the presented study, we show strongly enhanced (at least 10 times over the far field background) tip-enhanced Raman scattering (TERS) response from 1–4 L ReS2 on gold, which not only enables high spatial resolution in the TERS maps, but also remains, to a great extent, indifferent to the in-plane orientation of the ReS2 crystals. We attribute this orientation indifference to the fact that in the gap mode TERS configuration, the optical electric field is normal to the crystal plane. Additionally, we demonstrate in our TERS spectra the presence of low-frequency bands, the spectral position of which correlates with the local crystal layer number and matches very well previously published conventional Raman data, which allows a straightforward nanospectroscopic assessment of the layer number even in sub-micron-sized crystals.\u0000 </div>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 6","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148274808","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

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2026-04-30

引用次数: 0

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2026-04-26

引用次数: 0