@article{14687,
  abstract     = {The short history of research on Li-O2 batteries has seen a remarkable number of mechanistic U-turns over the years. From the initial use of carbonate electrolytes, that were then found to be entirely unsuitable, to the belief that (su)peroxide was solely responsible for degradation, before the more reactive singlet oxygen was found to form, to the hypothesis that capacity depends on a competing surface/solution mechanism before a practically exclusive solution mechanism was identified. Herein, we argue for an ever-fresh look at the reported data without bias towards supposedly established explanations. We explain how the latest findings on rate and capacity limits, as well as the origin of side reactions, are connected via the disproportionation (DISP) step in the (dis)charge mechanism. Therefrom, directions emerge for the design of electrolytes and mediators on how to suppress side reactions and to enable high rate and high reversible capacity.},
  author       = {Jethwa, Rajesh B and Mondal, Soumyadip and Pant, Bhargavi and Freunberger, Stefan Alexander},
  issn         = {1521-3773},
  journal      = {Angewandte Chemie International Edition},
  keywords     = {General Chemistry, Catalysis},
  number       = {28},
  publisher    = {Wiley},
  title        = {{To DISP or not? The far‐reaching reaction mechanisms underpinning Lithium‐air batteries}},
  doi          = {10.1002/anie.202316476},
  volume       = {63},
  year         = {2024},
}

@article{12113,
  abstract     = {The power factor of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) film can be significantly improved by optimizing the oxidation level of the film in oxidation and reduction processes. However, precise control over the oxidation and reduction effects in PEDOT:PSS remains a challenge, which greatly sacrifices both S and σ. Here, we propose a two-step post-treatment using a mixture of ethylene glycol (EG) and Arginine (Arg) and sulfuric acid (H2SO4) in sequence to engineer high-performance PEDOT:PSS thermoelectric films. The high-polarity EG dopant removes the excess non-ionized PSS and induces benzenoid-to-quinoid conformational change in the PEDOT:PSS films. In particular, basic amino acid Arg tunes the oxidation level of PEDOT:PSS and prevents the films from over-oxidation during H2SO4 post-treatment, leading to increased S. The following H2SO4 post-treatment further induces highly orientated lamellar stacking microstructures to increase σ, yielding a maximum power factor of 170.6 μW m−1 K−2 at 460 K. Moreover, a novel trigonal-shape thermoelectric device is designed and assembled by the as-prepared PEDOT:PSS films in order to harvest heat via a vertical temperature gradient. An output power density of 33 μW cm−2 is generated at a temperature difference of 40 K, showing the potential application for low-grade wearable electronic devices.},
  author       = {Zhang, Li and Liu, Xingyu and Wu, Ting and Xu, Shengduo and Suo, Guoquan and Ye, Xiaohui and Hou, Xiaojiang and Yang, Yanling and Liu, Qingfeng and Wang, Hongqiang},
  issn         = {0169-4332},
  journal      = {Applied Surface Science},
  keywords     = {Surfaces, Coatings and Films, Condensed Matter Physics, Surfaces and Interfaces, General Physics and Astronomy, General Chemistry},
  publisher    = {Elsevier},
  title        = {{Two-step post-treatment to deliver high performance thermoelectric device with vertical temperature gradient}},
  doi          = {10.1016/j.apsusc.2022.156101},
  volume       = {613},
  year         = {2023},
}

@article{13989,
  abstract     = {Characterizing and controlling entanglement in quantum materials is crucial for the development of next-generation quantum technologies. However, defining a quantifiable figure of merit for entanglement in macroscopic solids is theoretically and experimentally challenging. At equilibrium the presence of entanglement can be diagnosed by extracting entanglement witnesses from spectroscopic observables and a nonequilibrium extension of this method could lead to the discovery of novel dynamical phenomena. Here, we propose a systematic approach to quantify the time-dependent quantum Fisher information and entanglement depth of transient states of quantum materials with time-resolved resonant inelastic x-ray scattering. Using a quarter-filled extended Hubbard model as an example, we benchmark the efficiency of this approach and predict a light-enhanced many-body entanglement due to the proximity to a phase boundary. Our work sets the stage for experimentally witnessing and controlling entanglement in light-driven quantum materials via ultrafast spectroscopic measurements.},
  author       = {Hales, Jordyn and Bajpai, Utkarsh and Liu, Tongtong and Baykusheva, Denitsa Rangelova and Li, Mingda and Mitrano, Matteo and Wang, Yao},
  issn         = {2041-1723},
  journal      = {Nature Communications},
  keywords     = {General Physics and Astronomy, General Biochemistry, Genetics and Molecular Biology, General Chemistry, Multidisciplinary},
  publisher    = {Springer Nature},
  title        = {{Witnessing light-driven entanglement using time-resolved resonant inelastic X-ray scattering}},
  doi          = {10.1038/s41467-023-38540-3},
  volume       = {14},
  year         = {2023},
}

@article{12675,
  abstract     = {Aromatic side chains are important reporters of the plasticity of proteins, and often form important contacts in protein--protein interactions. By studying a pair of structurally homologous cross-β amyloid fibrils, HET-s and HELLF, with a specific isotope-labeling approach and magic-angle-spinning (MAS) NMR, we have characterized the dynamic behavior of Phe and Tyr aromatic rings to show that the hydrophobic amyloid core is rigid, without any sign of "breathing motions" over hundreds of milliseconds at least. Aromatic residues exposed at the fibril surface have a rigid ring axis but undergo ring flips, on a variety of time scales from ns to µs. Our approach provides direct insight into hydrophobic-core motions, enabling a better evaluation of the conformational heterogeneity generated from a NMR structural ensemble of such amyloid cross-β architecture.},
  author       = {Becker, Lea Marie and Berbon, Mélanie and Vallet, Alicia and Grelard, Axelle and Morvan, Estelle and Bardiaux, Benjamin and Lichtenecker, Roman and Ernst, Matthias and Loquet, Antoine and Schanda, Paul},
  issn         = {1521-3773},
  journal      = {Angewandte Chemie International Edition},
  keywords     = {General Chemistry, Catalysis},
  number       = {19},
  publisher    = {Wiley},
  title        = {{The rigid core and flexible surface of amyloid fibrils probed by Magic‐Angle Spinning NMR of aromatic residues}},
  doi          = {10.1002/anie.202219314},
  volume       = {62},
  year         = {2023},
}

@article{12920,
  abstract     = {The multicomponent approach allows to incorporate several functionalities into a single covalent organic framework (COF) and consequently allows the construction of bifunctional materials for cooperative catalysis. The well-defined structure of such multicomponent COFs is furthermore ideally suited for structure-activity relationship studies. We report a series of multicomponent COFs that contain acridine- and 2,2’-bipyridine linkers connected through 1,3,5-benzenetrialdehyde derivatives. The acridine motif is responsible for broad light absorption, while the bipyridine unit enables complexation of nickel catalysts. These features enable the usage of the framework materials as catalysts for light-mediated carbon−heteroatom cross-couplings. Variation of the node units shows that the catalytic activity correlates to the keto-enamine tautomer isomerism. This allows switching between high charge-carrier mobility and persistent, localized charge-separated species depending on the nodes, a tool to tailor the materials for specific reactions. Moreover, nickel-loaded COFs are recyclable and catalyze cross-couplings even using red light irradiation.},
  author       = {Traxler, Michael and Reischauer, Susanne and Vogl, Sarah and Roeser, Jérôme and Rabeah, Jabor and Penschke, Christopher and Saalfrank, Peter and Pieber, Bartholomäus and Thomas, Arne},
  issn         = {1521-3765},
  journal      = {Chemistry – A European Journal},
  keywords     = {General Chemistry, Catalysis, Organic Chemistry},
  number       = {4},
  publisher    = {Wiley},
  title        = {{Programmable photocatalytic activity of multicomponent covalent organic frameworks used as metallaphotocatalysts}},
  doi          = {10.1002/chem.202202967},
  volume       = {29},
  year         = {2023},
}

@article{12922,
  abstract     = {The 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 López‐Salas, Nieves},
  issn         = {1521-3773},
  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         = {2023},
}

@article{13216,
  abstract     = {Physical catalysts often have multiple sites where reactions can take place. One prominent example is single-atom alloys, where the reactive dopant atoms can preferentially locate in the bulk or at different sites on the surface of the nanoparticle. However, ab initio modeling of catalysts usually only considers one site of the catalyst, neglecting the effects of multiple sites. Here, nanoparticles of copper doped with single-atom rhodium or palladium are modeled for the dehydrogenation of propane. Single-atom alloy nanoparticles are simulated at 400–600 K, using machine learning potentials trained on density functional theory calculations, and then the occupation of different single-atom active sites is identified using a similarity kernel. Further, the turnover frequency for all possible sites is calculated for propane dehydrogenation to propene through microkinetic modeling using density functional theory calculations. The total turnover frequencies of the whole nanoparticle are then described from both the population and the individual turnover frequency of each site. Under operating conditions, rhodium as a dopant is found to almost exclusively occupy (111) surface sites while palladium as a dopant occupies a greater variety of facets. Undercoordinated dopant surface sites are found to tend to be more reactive for propane dehydrogenation compared to the (111) surface. It is found that considering the dynamics of the single-atom alloy nanoparticle has a profound effect on the calculated catalytic activity of single-atom alloys by several orders of magnitude.},
  author       = {Bunting, Rhys and Wodaczek, Felix and Torabi, Tina and Cheng, Bingqing},
  issn         = {1520-5126},
  journal      = {Journal of the American Chemical Society},
  keywords     = {Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis},
  number       = {27},
  pages        = {14894--14902},
  publisher    = {American Chemical Society},
  title        = {{Reactivity of single-atom alloy nanoparticles: Modeling the dehydrogenation of propane}},
  doi          = {10.1021/jacs.3c04030},
  volume       = {145},
  year         = {2023},
}

@article{13354,
  abstract     = {Integrating light-sensitive molecules within nanoparticle (NP) assemblies is an attractive approach to fabricate new photoresponsive nanomaterials. Here, we describe the concept of photocleavable anionic glue (PAG): small trianions capable of mediating interactions between (and inducing the aggregation of) cationic NPs by means of electrostatic interactions. Exposure to light converts PAGs into dianionic products incapable of maintaining the NPs in an assembled state, resulting in light-triggered disassembly of NP aggregates. To demonstrate the proof-of-concept, we work with an organic PAG incorporating the UV-cleavable o-nitrobenzyl moiety and an inorganic PAG, the photosensitive trioxalatocobaltate(III) complex, which absorbs light across the entire visible spectrum. Both PAGs were used to prepare either amorphous NP assemblies or regular superlattices with a long-range NP order. These NP aggregates disassembled rapidly upon light exposure for a specific time, which could be tuned by the incident light wavelength or the amount of PAG used. Selective excitation of the inorganic PAG in a system combining the two PAGs results in a photodecomposition product that deactivates the organic PAG, enabling nontrivial disassembly profiles under a single type of external stimulus.},
  author       = {Wang, Jinhua and Peled, Tzuf Shay and Klajn, Rafal},
  issn         = {1520-5126},
  journal      = {Journal of the American Chemical Society},
  keywords     = {Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis},
  number       = {7},
  pages        = {4098--4108},
  publisher    = {American Chemical Society},
  title        = {{Photocleavable anionic glues for light-responsive nanoparticle aggregates}},
  doi          = {10.1021/jacs.2c11973},
  volume       = {145},
  year         = {2023},
}

@misc{14861,
  abstract     = {Cover Page},
  author       = {Becker, Lea Marie and Berbon, Mélanie and Vallet, Alicia and Grelard, Axelle and Morvan, Estelle and Bardiaux, Benjamin and Lichtenecker, Roman and Ernst, Matthias and Loquet, Antoine and Schanda, Paul},
  booktitle    = {Angewandte Chemie International Edition},
  issn         = {1521-3773},
  keywords     = {General Chemistry, Catalysis},
  number       = {19},
  publisher    = {Wiley},
  title        = {{Cover Picture: The rigid core and flexible surface of amyloid fibrils probed by Magic‐Angle‐Spinning NMR spectroscopy of aromatic residues}},
  doi          = {10.1002/anie.202304138},
  volume       = {62},
  year         = {2023},
}

@article{11951,
  abstract     = {The mammalian hippocampal formation (HF) plays a key role in several higher brain functions, such as spatial coding, learning and memory. Its simple circuit architecture is often viewed as a trisynaptic loop, processing input originating from the superficial layers of the entorhinal cortex (EC) and sending it back to its deeper layers. Here, we show that excitatory neurons in layer 6b of the mouse EC project to all sub-regions comprising the HF and receive input from the CA1, thalamus and claustrum. Furthermore, their output is characterized by unique slow-decaying excitatory postsynaptic currents capable of driving plateau-like potentials in their postsynaptic targets. Optogenetic inhibition of the EC-6b pathway affects spatial coding in CA1 pyramidal neurons, while cell ablation impairs not only acquisition of new spatial memories, but also degradation of previously acquired ones. Our results provide evidence of a functional role for cortical layer 6b neurons in the adult brain.},
  author       = {Ben Simon, Yoav and Käfer, Karola and Velicky, Philipp and Csicsvari, Jozsef L and Danzl, Johann G and Jonas, Peter M},
  issn         = {2041-1723},
  journal      = {Nature Communications},
  keywords     = {General Physics and Astronomy, General Biochemistry, Genetics and Molecular Biology, General Chemistry, Multidisciplinary},
  publisher    = {Springer Nature},
  title        = {{A direct excitatory projection from entorhinal layer 6b neurons to the hippocampus contributes to spatial coding and memory}},
  doi          = {10.1038/s41467-022-32559-8},
  volume       = {13},
  year         = {2022},
}

@article{12130,
  abstract     = {Germline determination is essential for species survival and evolution in multicellular organisms. In most flowering plants, formation of the female germline is initiated with specification of one megaspore mother cell (MMC) in each ovule; however, the molecular mechanism underlying this key event remains unclear. Here we report that spatially restricted auxin signaling promotes MMC fate in Arabidopsis. Our results show that the microRNA160 (miR160) targeted gene ARF17 (AUXIN RESPONSE FACTOR17) is required for promoting MMC specification by genetically interacting with the SPL/NZZ (SPOROCYTELESS/NOZZLE) gene. Alterations of auxin signaling cause formation of supernumerary MMCs in an ARF17- and SPL/NZZ-dependent manner. Furthermore, miR160 and ARF17 are indispensable for attaining a normal auxin maximum at the ovule apex via modulating the expression domain of PIN1 (PIN-FORMED1) auxin transporter. Our findings elucidate the mechanism by which auxin signaling promotes the acquisition of female germline cell fate in plants.},
  author       = {Huang, Jian and Zhao, Lei and Malik, Shikha and Gentile, Benjamin R. and Xiong, Va and Arazi, Tzahi and Owen, Heather A. and Friml, Jiří and Zhao, Dazhong},
  issn         = {2041-1723},
  journal      = {Nature Communications},
  keywords     = {General Physics and Astronomy, General Biochemistry, Genetics and Molecular Biology, General Chemistry, Multidisciplinary},
  publisher    = {Springer Nature},
  title        = {{Specification of female germline by microRNA orchestrated auxin signaling in Arabidopsis}},
  doi          = {10.1038/s41467-022-34723-6},
  volume       = {13},
  year         = {2022},
}

@article{12208,
  abstract     = {The inadequate understanding of the mechanisms that reversibly convert molecular sulfur (S) into lithium sulfide (Li<jats:sub>2</jats:sub>S) via soluble polysulfides (PSs) formation impedes the development of high-performance lithium-sulfur (Li-S) batteries with non-aqueous electrolyte solutions. Here, we use operando small and wide angle X-ray scattering and operando small angle neutron scattering (SANS) measurements to track the nucleation, growth and dissolution of solid deposits from atomic to sub-micron scales during real-time Li-S cell operation. In particular, stochastic modelling based on the SANS data allows quantifying the nanoscale phase evolution during battery cycling. We show that next to nano-crystalline Li<jats:sub>2</jats:sub>S the deposit comprises solid short-chain PSs particles. The analysis of the experimental data suggests that initially, Li<jats:sub>2</jats:sub>S<jats:sub>2</jats:sub> precipitates from the solution and then is partially converted via solid-state electroreduction to Li<jats:sub>2</jats:sub>S. We further demonstrate that mass transport, rather than electron transport through a thin passivating film, limits the discharge capacity and rate performance in Li-S cells.},
  author       = {Prehal, Christian and von Mentlen, Jean-Marc and Drvarič Talian, Sara and Vizintin, Alen and Dominko, Robert and Amenitsch, Heinz and Porcar, Lionel and Freunberger, Stefan Alexander and Wood, Vanessa},
  issn         = {2041-1723},
  journal      = {Nature Communications},
  keywords     = {General Physics and Astronomy, General Biochemistry, Genetics and Molecular Biology, General Chemistry, Multidisciplinary},
  publisher    = {Springer Nature},
  title        = {{On the nanoscale structural evolution of solid discharge products in lithium-sulfur batteries using operando scattering}},
  doi          = {10.1038/s41467-022-33931-4},
  volume       = {13},
  year         = {2022},
}

@article{12217,
  abstract     = {The development dynamics and self-organization of glandular branched epithelia is of utmost importance for our understanding of diverse processes ranging from normal tissue growth to the growth of cancerous tissues. Using single primary murine pancreatic ductal adenocarcinoma (PDAC) cells embedded in a collagen matrix and adapted media supplementation, we generate organoids that self-organize into highly branched structures displaying a seamless lumen connecting terminal end buds, replicating in vivo PDAC architecture. We identify distinct morphogenesis phases, each characterized by a unique pattern of cell invasion, matrix deformation, protein expression, and respective molecular dependencies. We propose a minimal theoretical model of a branching and proliferating tissue, capturing the dynamics of the first phases. Observing the interaction of morphogenesis, mechanical environment and gene expression in vitro sets a benchmark for the understanding of self-organization processes governing complex organoid structure formation processes and branching morphogenesis.},
  author       = {Randriamanantsoa, S. and Papargyriou, A. and Maurer, H. C. and Peschke, K. and Schuster, M. and Zecchin, G. and Steiger, K. and Öllinger, R. and Saur, D. and Scheel, C. and Rad, R. and Hannezo, Edouard B and Reichert, M. and Bausch, A. R.},
  issn         = {2041-1723},
  journal      = {Nature Communications},
  keywords     = {General Physics and Astronomy, General Biochemistry, Genetics and Molecular Biology, General Chemistry, Multidisciplinary},
  publisher    = {Springer Nature},
  title        = {{Spatiotemporal dynamics of self-organized branching in pancreas-derived organoids}},
  doi          = {10.1038/s41467-022-32806-y},
  volume       = {13},
  year         = {2022},
}

@article{12228,
  abstract     = {The question of how RNA, as the principal carrier of genetic information evolved is fundamentally important for our understanding of the origin of life. The RNA molecule is far too complex to have formed in one evolutionary step, suggesting that ancestral proto-RNAs (first ancestor of RNA) may have existed, which evolved over time into the RNA of today. Here we show that isoxazole nucleosides, which are quickly formed from hydroxylamine, cyanoacetylene, urea and ribose, are plausible precursors for RNA. The isoxazole nucleoside can rearrange within an RNA-strand to give cytidine, which leads to an increase of pairing stability. If the proto-RNA contains a canonical seed-nucleoside with defined stereochemistry, the seed-nucleoside can control the configuration of the anomeric center that forms during the in-RNA transformation. The results demonstrate that RNA could have emerged from evolutionarily primitive precursor isoxazole ribosides after strand formation.},
  author       = {Xu, Felix and Crisp, Antony and Schinkel, Thea and Dubini, Romeo C. A. and Hübner, Sarah and Becker, Sidney and Schelter, Florian and Rovo, Petra and Carell, Thomas},
  issn         = {1521-3773},
  journal      = {Angewandte Chemie International Edition},
  keywords     = {General Chemistry, Catalysis},
  number       = {45},
  publisher    = {Wiley},
  title        = {{Isoxazole nucleosides as building blocks for a plausible proto‐RNA}},
  doi          = {10.1002/anie.202211945},
  volume       = {61},
  year         = {2022},
}

@article{13993,
  abstract     = {Photoionization is a process taking place on attosecond time scales. How its properties evolve from isolated particles to the condensed phase is an open question of both fundamental and practical relevance. Here, we review recent work that has advanced the study of photoionization dynamics from atoms to molecules, clusters and the liquid phase. The first measurements of molecular photoionization delays have revealed the attosecond dynamics of electron emission from a molecular shape resonance and their sensitivity to the molecular potential. Using electron-ion coincidence spectroscopy these measurements have been extended from isolated molecules to clusters. A continuous increase of the delays with the water-cluster size has been observed up to a size of 4-5 molecules, followed by a saturation towards larger clusters. Comparison with calculations has revealed a correlation of the time delay with the spatial extension of the created electron hole. Using cylindrical liquid-microjet techniques, these measurements have also been extended to liquid water, revealing a delay relative to isolated water molecules that was very similar to the largest water clusters studied. Detailed modeling based on Monte-Carlo simulations confirmed that these delays are dominated by the contributions of the first two solvation shells, which agrees with the results of the cluster measurements. These combined results open the perspective of experimentally characterizing the delocalization of electronic wave functions in complex systems and studying their evolution on attosecond time scales.},
  author       = {Gong, Xiaochun and Jordan, Inga and Huppert, Martin and Heck, Saijoscha and Baykusheva, Denitsa Rangelova and Jelovina, Denis and Schild, Axel and Wörner, Hans Jakob},
  issn         = {2673-2424},
  journal      = {Chimia},
  keywords     = {General Medicine, General Chemistry},
  number       = {6},
  pages        = {520--528},
  publisher    = {Swiss Chemical Society},
  title        = {{Attosecond photoionization dynamics: from molecules over clusters to the liquid phase}},
  doi          = {10.2533/chimia.2022.520},
  volume       = {76},
  year         = {2022},
}

@article{12923,
  abstract     = {Photoredox-mediated Ni-catalyzed cross-couplings are powerful transformations to form carbon–heteroatom bonds and are generally photocatalyzed by noble metal complexes. Low-cost and easy-to-prepare carbon dots (CDs) are attractive quasi-homogeneous photocatalyst alternatives, but their applicability is limited by their short photoluminescence (PL) lifetimes. By tuning the surface and PL properties of CDs, we designed colloidal CD nano-photocatalysts for a broad range of Ni-mediated cross-couplings between aryl halides and nucleophiles. In particular, a CD decorated with amino groups permitted coupling to a wide range of aryl halides and thiols under mild, base-free conditions. Mechanistic studies suggested dynamic quenching of the CD excited state by the Ni co-catalyst and identified that pyridinium iodide (pyHI), a previously used additive in metallaphotocatalyzed cross-couplings, can also act as a photocatalyst in such transformations.},
  author       = {Zhao, Zhouxiang and Pieber, Bartholomäus and Delbianco, Martina},
  issn         = {2155-5435},
  journal      = {ACS Catalysis},
  keywords     = {Catalysis, General Chemistry},
  number       = {22},
  pages        = {13831--13837},
  publisher    = {American Chemical Society},
  title        = {{Modulating the surface and photophysical properties of carbon dots to access colloidal photocatalysts for cross-couplings}},
  doi          = {10.1021/acscatal.2c04025},
  volume       = {12},
  year         = {2022},
}

@article{12924,
  abstract     = {We demonstrate that several visible-light-mediated carbon−heteroatom cross-coupling reactions can be carried out using a photoactive NiII precatalyst that forms in situ from a nickel salt and a bipyridine ligand decorated with two carbazole groups (Ni(Czbpy)Cl2). The activation of this precatalyst towards cross-coupling reactions follows a hitherto undisclosed mechanism that is different from previously reported light-responsive nickel complexes that undergo metal-to-ligand charge transfer. Theoretical and spectroscopic investigations revealed that irradiation of Ni(Czbpy)Cl2 with visible light causes an initial intraligand charge transfer event that triggers productive catalysis. Ligand polymerization affords a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross-coupling reactions. The heterogeneous catalyst shows stable performance in a packed-bed flow reactor during a week of continuous operation.},
  author       = {Cavedon, Cristian and Gisbertz, Sebastian and Reischauer, Susanne and Vogl, Sarah and Sperlich, Eric and Burke, John H. and Wallick, Rachel F. and Schrottke, Stefanie and Hsu, Wei‐Hsin and Anghileri, Lucia and Pfeifer, Yannik and Richter, Noah and Teutloff, Christian and Müller‐Werkmeister, Henrike and Cambié, Dario and Seeberger, Peter H. and Vura‐Weis, Josh and van der Veen, Renske M. and Thomas, Arne and Pieber, Bartholomäus},
  issn         = {1521-3773},
  journal      = {Angewandte Chemie International Edition},
  keywords     = {General Chemistry, Catalysis},
  number       = {46},
  publisher    = {Wiley},
  title        = {{Intraligand charge transfer enables visible‐light‐mediated Nickel‐catalyzed cross-coupling reactions}},
  doi          = {10.1002/anie.202211433},
  volume       = {61},
  year         = {2022},
}

@article{13347,
  abstract     = {Confining molecules within well-defined nanosized spaces can profoundly alter their physicochemical characteristics. For example, the controlled aggregation of chromophores into discrete oligomers has been shown to tune their optical properties whereas encapsulation of reactive species within molecular hosts can increase their stability. The resazurin/resorufin pair has been widely used for detecting redox processes in biological settings; yet, how tight confinement affects the properties of these two dyes remains to be explored. Here, we show that a flexible Pd<jats:sup>II</jats:sup><jats:sub>6</jats:sub>L<jats:sub>4</jats:sub> coordination cage can efficiently encapsulate both resorufin and resazurin in the form of dimers, dramatically modulating their optical properties. Furthermore, binding within the cage significantly decreases the reduction rate of resazurin to resorufin, and the rate of the subsequent reduction of resorufin to dihydroresorufin. During our studies, we also found that upon dilution, the Pd<jats:sup>II</jats:sup><jats:sub>6</jats:sub>L<jats:sub>4</jats:sub> cage disassembles to afford Pd<jats:sup>II</jats:sup><jats:sub>2</jats:sub>L<jats:sub>2</jats:sub> species, which lacks the ability to form inclusion complexes – a process that can be reversed upon the addition of the strongly binding resorufin/resazurin guests. We expect that the herein disclosed ability of a water-soluble cage to reversibly modulate the optical and chemical properties of a molecular redox probe will expand the versatility of synthetic fluorescent probes in biologically relevant environments.},
  author       = {Yanshyna, Oksana and Białek, Michał J. and Chashchikhin, Oleg V. and Klajn, Rafal},
  issn         = {2399-3669},
  journal      = {Communications Chemistry},
  keywords     = {Materials Chemistry, Biochemistry, Environmental Chemistry, General Chemistry},
  publisher    = {Springer Nature},
  title        = {{Encapsulation within a coordination cage modulates the reactivity of redox-active dyes}},
  doi          = {10.1038/s42004-022-00658-8},
  volume       = {5},
  year         = {2022},
}

@article{13348,
  abstract     = {Molecular confinement effects can profoundly alter the physicochemical properties of the confined species. A plethora of organic molecules were encapsulated within the cavities of supramolecular hosts, and the impact of the cavity size and polarity was widely investigated. However, the extent to which the properties of the confined guests can be affected by the symmetry of the cage─which dictates the shape of the cavity─remains to be understood. Here we show that cage symmetry has a dramatic effect on the equilibrium between two isomers of the encapsulated spiropyran guests. Working with two Pd-based coordination cages featuring similarly sized but differently shaped hydrophobic cavities, we found a highly selective stabilization of the isomer whose shape matches that of the cavity of the cage. A Td-symmetric cage stabilized the spiropyrans’ colorless form and rendered them photochemically inert. In contrast, a D2h-symmetric cage favored the colored isomer, while maintaining reversible photoswitching between the two states of the encapsulated spiropyrans. We also show that the switching kinetics strongly depend on the substitution pattern on the spiropyran scaffold. This finding was used to fabricate a time-sensitive information storage medium with tunable lifetimes of the encoded messages.},
  author       = {Wang, Jinhua and Avram, Liat and Diskin-Posner, Yael and Białek, Michał J. and Stawski, Wojciech and Feller, Moran and Klajn, Rafal},
  issn         = {1520-5126},
  journal      = {Journal of the American Chemical Society},
  keywords     = {Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis},
  number       = {46},
  pages        = {21244--21254},
  publisher    = {American Chemical Society},
  title        = {{Altering the properties of spiropyran switches using coordination cages with different symmetries}},
  doi          = {10.1021/jacs.2c08901},
  volume       = {144},
  year         = {2022},
}

@article{13350,
  abstract     = {Confinement within molecular cages can dramatically modify the physicochemical properties of the encapsulated guest molecules, but such host-guest complexes have mainly been studied in a static context. Combining confinement effects with fast guest exchange kinetics could pave the way toward stimuli-responsive supramolecular systems—and ultimately materials—whose desired properties could be tailored “on demand” rapidly and reversibly. Here, we demonstrate rapid guest exchange between inclusion complexes of an open-window coordination cage that can simultaneously accommodate two guest molecules. Working with two types of guests, anthracene derivatives and BODIPY dyes, we show that the former can substantially modify the optical properties of the latter upon noncovalent heterodimer formation. We also studied the light-induced covalent dimerization of encapsulated anthracenes and found large effects of confinement on reaction rates. By coupling the photodimerization with the rapid guest exchange, we developed a new way to modulate fluorescence using external irradiation.},
  author       = {Gemen, Julius and Białek, Michał J. and Kazes, Miri and Shimon, Linda J.W. and Feller, Moran and Semenov, Sergey N. and Diskin-Posner, Yael and Oron, Dan and Klajn, Rafal},
  issn         = {2451-9294},
  journal      = {Chem},
  keywords     = {Materials Chemistry, Biochemistry (medical), General Chemical Engineering, Environmental Chemistry, Biochemistry, General Chemistry},
  number       = {9},
  pages        = {2362--2379},
  publisher    = {Elsevier},
  title        = {{Ternary host-guest complexes with rapid exchange kinetics and photoswitchable fluorescence}},
  doi          = {10.1016/j.chempr.2022.05.008},
  volume       = {8},
  year         = {2022},
}