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This study investigates the catalytic effects of external electric fields (EEFs) on two reactions in solution: the Menshutkin reaction and the Chapman rearrangement. Utilizing a scanning tunneling microscope-based break-junction (STM-BJ) setup and monitoring reaction rates through high-performance liquid chromatography connected to a UV detector (HPLC-UV) and ultraperformance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-q-ToF-MS), we observed no rate enhancement for either reaction under ambient conditions. Density functional theory (DFT) calculations indicate that electric field-induced changes in reactant orientation and the minimization of activation energy are crucial factors in determining the efficacy of EEF-driven catalysis. Our findings suggest that the current experimental setups and field strengths are insufficient to catalyze these reactions, underscoring the importance of these criteria in assessing the reaction candidates.

We report an electrochemical method for doping two-dimensional (2D) superatomic semiconductor Re 6 Se 8 Cl 2 that significantly improves the material's electrical transport while retaining the in-plane and stacking structures. The electrochemical reduction induces the complete dissociation of chloride anions from the surface of each superatomic nanosheet. After the material is dehalogenated, we observe the electrical conductivity ( σ ) increases by two orders of magnitude while the 3D electron carrier density ( n 3D ) increases by three orders of magnitude. In addition, the thermal activation energy ( E a ) and electron mobility ( μ e ) decrease. We conclude that we have achieved effective electron-doping in 2D superatomic Re 6 Se 8 Cl 2 , which significantly improves the electrical transport properties. Our work sets the foundation for electrochemically doping and tuning the transport properties of other 2D superatomic materials.

Single-molecule one-dimensional topological insulator (1D TI) is a class of molecular wires that exhibit increasing conductance with wire length. This unique trend is due to the coupling between the two low-lying topological edge states of 1D TIs described by the Su-Schrieffer-Heeger model. In principle, this quantum phenomenon within 1D TIs can be utilized to achieve long-range gating in molecular conductors. Here, we study electron transport through a single-edge state of doubly oxidized oligophenylene bis(triarylamine) to understand the effect of the edge state coupling on conductance. We find that conductance is elevated by approximately 1 order of magnitude compared to a control molecule with the same conductance pathway. Density function theory calculations further support that the increase in conductance is due to the interaction between the edge states of 1D TIs. This work demonstrates a new gating paradigm in molecular electronics, while also providing a deeper understanding of how edge states interact and affect electron transport within 1D TIs.

A new method is reported to make air-stable n-type organic mixed ionic-electronic conductor (OMIEC) films for organic electrochemical transistors (OECTs) using a solution-processable small molecule helical perylene diimide trimer, hPDI[3]-C 11 . Alkyl side chains are attached to the conjugated core for processability and film making, which are then cleaved via thermal annealing. After the sidechains are removed, the hPDI[3] film becomes less hydrophobic, more ordered, and has a deeper lowest unoccupied molecular orbital (LUMO). These features provide improved ionic transport, greater electronic mobility, and increased stability in air and in aqueous solution. Subsequently, hPDI[3]-H is used as the active material in OECTs and a device with a transconductance of 44 mS, volumetric capacitance of ≈250 F cm -3 , µC * value of 1 F cm -1 V -1 s -1 , and excellent stability (> 5 weeks) is demonstrated. As proof of their practical applications, a hPDI[3]-H-based OECTs as a glucose sensor and electrochemical inverter is utilized. The approach of side chain removal after film formation charts a path to a wide range of molecular semiconductors to be used as stable, mixed ionic-electronic conductors., (© 2024 Wiley‐VCH GmbH.)

Recent studies have demonstrated that the mechanisms through which biopolymers like RNA interconvert between multiple folded structures are critical for their cellular functions. A major obstacle to elucidating these mechanisms is the lack of experimental approaches that can resolve these interconversions between functionally relevant biomolecular structures. Here, using a nano-electronic device with microsecond time resolution, we dissect the complete set of structural rearrangements executed by an ultra-stable RNA, the UUCG stem-loop, at the single-molecule level. We show that the stem-loop samples at least four conformations along two folding pathways leading to two distinct folded structures, only one of which has been previously observed. By modulating its flexibility, the stem-loop can adaptively select between these pathways, enabling it to both fold rapidly and resist unfolding. This paradigm of stabilization through compensatory changes in flexibility broadens our understanding of stable RNA structures and is expected to serve as a general strategy employed by all biopolymers., Competing Interests: Competing Interests D.G.L. and K.L.S. have a financial interest in Quicksilver Biosciences, Inc., which is commercializing smFET technology for molecular diagnostic applications. The other authors declare no competing financial interest.

Spin-polarized electrons can improve the efficiency and selectivity of photo- and electro-catalytic reactions, as demonstrated in the past with magnetic or magnetized catalysts. Here, we present a scheme in which spin-polarized charge separation occurs at the interfaces of nonmagnetic semiconductors and molecular films in the absence of a magnetic field. We take advantage of the spin-valley-locked band structure and valley-dependent optical selection rule in group VI transition metal dichalcogenide (TMDC) monolayers to generate spin-polarized electron-hole pairs. Photoinduced electron transfer from WS 2 to fullerene (C 60 ) and hole transfer from MoSe 2 to phthalocyanine (H 2 Pc) are found to result in spin polarization lifetimes that are 1 order of magnitude longer than those in the TMDC monolayers alone. Our findings connect valleytronic properties of TMDC monolayers to spin-polarized interfacial charge transfer and suggest a viable route toward spin-selective photocatalysis.

The successful incorporation of molecules as active circuit elements relies on the ability to tune their electronic properties through chemical design. A synthetic strategy that has been used to manipulate and gate circuit conductance involves attaching a pendant substituent along the molecular conduction pathway. However, such a chemical gate has not yet been shown to significantly modify conductance. Here, we report a novel series of triarylmethylium and triangulenium carbocations gated by different substituents coupled to the delocalized conducting orbitals on the molecular backbone through a Fano resonance. By changing the pendant substituents to modulate the position of the Fano resonance and its coupling to the conducting orbitals, we can regulate the junction conductance by a remarkable factor of 450. This work thus provides a new design principle to enable effective chemical gating of single-molecule devices toward effective molecular transistors.

Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid-state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representative superatom, Co 6 Se 8 (PEt 3 ) 6 . We probed its structural, electronic, and magnetic properties and revealed its detailed electronic structure as valence electrons delocalize over inorganic [Co 6 Se 8 ] core while ligands function as an insulated shell. 59 Co SSNMR measurements on the core and 31 P, 13 C on the ligands show that the neutral Co 6 Se 8 (PEt 3 ) 6 is diamagnetic and symmetric, with all ligands magnetically equivalent. Quantum computations cross-validate NMR results and reveal degenerate delocalized HOMO orbitals, indicating aromaticity. Ligand substitution keeps the inorganic core nearly intact. After losing one electron, the unpaired electron in [Co 6 Se 8 (PEt 3 ) 6 ] +1 is delocalized, causing paramagnetism and a delocalized electron spin. Notably, this feature of electron/spin delocalization over a large cluster is attractive for special single-electron devices., (© 2023 Wiley-VCH GmbH.)

Here we unveil a chiral molecular redox switch derived from PDI-based twistacenes─ c hPDI[2] that has the remarkable attributes of high-intensity and a broadband chiral response. This material exhibits facile, stable, and reversible multistate chiroptical switching behavior over a broad active wavelength range close to 700 nm, encompassing ultraviolet, visible, and near-infrared regions. Upon reduction, c hPDI[2] exhibits a substantial increase in the amplitude of its circular dichroic response, with an outstanding |ΔΔε| > 300 M -1 cm -1 and a high dissymmetry factor of 3 × 10 -2 at 960 nm. DFT calculations suggest that the long wavelength CD signal for doubly reduced c hPDI[2] originates from excitation of the PDI backbone to the π* orbital of the bridging alkene. Importantly, the dimer's molecular contortion facilitates ionic diffusion, enabling chiral switching in solid state films. The high dissymmetry factors and near-infrared response establish c hPDI[2] as a unique chiroptic switch.

Two-dimensional antiferromagnets have garnered considerable interest for the next generation of functional spintronics. However, many bulk materials from which two-dimensional antiferromagnets are isolated are limited by their air sensitivity, low ordering temperatures, and insulating transport properties. TaFe 1+ y Te 3 aims to address these challenges with increased air stability, metallic transport, and robust antiferromagnetism. Here, we synthesize TaFe 1+ y Te 3 ( y = 0.14), identify its structural, magnetic, and electronic properties, and elucidate the relationships between them. Axial-dependent high-field magnetization measurements on TaFe 1.14 Te 3 reveal saturation magnetic fields ranging between 27 and 30 T with saturation magnetic moments of 2.05-2.12 μ B . Magnetotransport measurements confirm that TaFe 1.14 Te 3 is metallic with strong coupling between magnetic order and electronic transport. Angle-resolved photoemission spectroscopy measurements across the magnetic transition uncover a complex interplay between itinerant electrons and local magnetic moments that drives the magnetic transition. We demonstrate the ability to isolate few-layer sheets of TaFe 1.14 Te 3 , establishing TaFe 1.14 Te 3 as a potential platform for two-dimensional spintronics.

Incorporating perylene diimide (PDI) units into helicene structures has become a useful strategy for giving access to non-planar electron acceptors as well as a method of creating molecules with unique and intriguing chiroptical properties. This minireview describes this fusion of PDIs with helicenes., (© 2023 Wiley Periodicals LLC.)

Radicals are unique molecular systems for applications in electronic devices due to their open-shell electronic structures. Radicals can function as good electrical conductors and switches in molecular circuits while also holding great promise in the field of molecular spintronics. However, it is both challenging to create stable, persistent radicals and to understand their properties in molecular junctions. The goal of this Perspective is to address this dual challenge by providing design principles for the synthesis of stable radicals relevant to molecular junctions, as well as offering current insight into the electronic properties of radicals in single-molecule devices. By exploring both the chemical and physical properties of established radical systems, we will facilitate increased exploration and development of radical-based molecular systems.

Molecular one-dimensional topological insulators (1D TIs), described by the Su-Schrieffer-Heeger (SSH) model, are a new class of molecular electronic wires whose low-energy topological edge states endow them with high electrical conductivity. However, when these 1D TIs become long, the high conductance is not sustained because the coupling between the edge states decreases with increasing length. Here, we present a new design where we connect multiple short 1D SSH TI units linearly or in a cycle to create molecular wires with a continuous topological state density. Using a tight-binding method, we show that the linear system gives a length-independent conductance. The cyclic systems show an interesting odd-even effect, with unit transmission in the topological limit, but zero transmission in the trivial limit. Furthermore, based on our calculations, we predict that these systems can support resonant transmission with a quantum of conductance. We can further expand these results to phenylene-based linear and cyclic 1D TI systems and confirm the length-dependent conductance in such systems.

We advance the chemistry of apical chlorine substitution in the 2D superatomic semiconductor Re 6 Se 8 Cl 2 to build functional and atomically precise monolayers on the surface of the 2D superatomic Re 6 Se 8 substrate. We create a functional monolayer by installing surface (2,2'-bipyridine)-4-sulfide (Sbpy) groups that chelate to catalytically active metal complexes. Through this reaction chemistry, we can create monolayers where we can control the distribution of catalytic sites. As a demonstration, we create highly active electrocatalysts for the oxygen evolution reaction using monolayers of cobalt(acetylacetonate) 2 bipyridine. We can further produce a series of catalysts by incorporating organic spacers in the functional monolayers. The structure and flexibility of the surface linkers can affect the catalytic performance, possibly by tuning the coupling between the functional monolayer and the superatomic substrate. These studies establish that the Re 6 Se 8 sheet behaves as a chemical pegboard: a surface amenable to geometrically and chemically well-defined modification to yield functional monolayers, in this case catalytically active, that are atomically precise. This is an effective method to generate diverse families of functional nanomaterials.

Molecular one-dimensional topological insulators (1D TIs), which conduct through energetically low-lying topological edge states, can be extremely highly conducting and exhibit a reversed conductance decay, affording them great potential as building blocks for nanoelectronic devices. However, these properties can only be observed at the short length limit. To extend the length at which these anomalous effects can be observed, we design topological oligo[ n ]emeraldine wires using short 1D TIs as building blocks. As the wire length increases, the number of topological states increases, enabling an increased electronic transmission along the wire; specifically, we show that we can drive over a microampere current through a single ∼5 nm molecular wire, appreciably more than what has been observed in other long wires reported to date. Calculations and experiments show that the longest oligo[7]emeraldine with doped topological states has over 10 6 enhancements in the transmission compared to its pristine form. The discovery of these highly conductive, long organic wires helps overcome a fundamental hurdle to implementing molecules in complex, nanoscale circuitry: their structures become too insulating at lengths that are useful in designing nanoscale circuits.

Electric fields have been used to control and direct chemical reactions in biochemistry and enzymatic catalysis, yet directly applying external electric fields to activate reactions in bulk solution and to characterize them ex situ remains a challenge. Here we utilize the scanning tunneling microscope-based break-junction technique to investigate the electric field driven homolytic cleavage of the radical initiator 4-(methylthio)benzoic peroxyanhydride at ambient temperatures in bulk solution, without the use of co-initiators or photochemical activators. Through time-dependent ex situ quantification by high performance liquid chromatography using a UV-vis detector, we find that the electric field catalyzes the reaction. Importantly, we demonstrate that the reaction rate in a field increases linearly with the solvent dielectric constant. Using density functional theory calculations, we show that the applied electric field decreases the dissociation energy of the O-O bond and stabilizes the product relative to the reactant due to their different dipole moments., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Interest in cultivating cannabis for medical and recreational purposes is increasing due to a dramatic shift in cannabis legislation worldwide. Therefore, a comprehensive understanding of the composition of secondary metabolites, cannabinoids, and terpenes grown in different environmental conditions is of primary importance for the medical and recreational use of cannabis. We compared the terpene and cannabinoid profiles using gas/liquid chromatography and mass spectrometry for commercial cannabis from genetically identical plants grown indoors using artificial light and artificially grown media or outdoors grown in living soil and natural sunlight. By analyzing the cannabinoids, we found significant variations in the metabolomic profile of cannabis for the different environments. Overall, for both cultivars, there were significantly greater oxidized and degraded cannabinoids in the indoor-grown samples. Moreover, the outdoor-grown samples had significantly more unusual cannabinoids, such as C4- and C6-THCA. There were also significant differences in the terpene profiles between indoor- and outdoor-grown cannabis. The outdoor samples had a greater preponderance of sesquiterpenes including β-caryophyllene, α-humulene, α-bergamotene, α-guaiene, and germacrene B relative to the indoor samples.

We have developed and used single-molecule field-effect transistors (smFETs) to characterize the conformational free-energy landscape of RNA stem-loops. Stem-loops are one of the most common RNA structural motifs and serve as building blocks for the formation of complex RNA structures. Given their prevalence and integral role in RNA folding, the kinetics of stem-loop (un)folding has been extensively characterized using both experimental and computational approaches. Interestingly, these studies have reported vastly disparate timescales of (un)folding, which has been interpreted as evidence that (un)folding of even simple stem-loops occurs on a highly rugged conformational energy landscape. Because smFETs do not rely on fluorophore reporters of conformation or mechanical (un)folding forces, they provide a unique approach that has allowed us to directly monitor tens of thousands of (un)folding events of individual stem-loops at a 200 μs time resolution. Our results show that under our experimental conditions, stem-loops (un)fold over a 1-200 ms timescale during which they transition between ensembles of unfolded and folded conformations, the latter of which is composed of at least two sub-populations. The 1-200 ms timescale of (un)folding we observe here indicates that smFETs report on complete (un)folding trajectories in which unfolded conformations of the RNA spend long periods of time wandering the free-energy landscape before sampling one of several misfolded conformations or the natively folded conformation. Our findings highlight the extremely rugged landscape on which even the simplest RNA structural elements fold and demonstrate that smFETs are a unique and powerful approach for characterizing the conformational free-energy of RNA.

The two natural allotropes of carbon, diamond and graphite, are extended networks of sp 3 -hybridized and sp 2 -hybridized atoms, respectively 1 . By mixing different hybridizations and geometries of carbon, one could conceptually construct countless synthetic allotropes. Here we introduce graphullerene, a two-dimensional crystalline polymer of C 60 that bridges the gulf between molecular and extended carbon materials. Its constituent fullerene subunits arrange hexagonally in a covalently interconnected molecular sheet. We report charge-neutral, purely carbon-based macroscopic crystals that are large enough to be mechanically exfoliated to produce molecularly thin flakes with clean interfaces-a critical requirement for the creation of heterostructures and optoelectronic devices 2 . The synthesis entails growing single crystals of layered polymeric (Mg 4 C 60 ) ∞ by chemical vapour transport and subsequently removing the magnesium with dilute acid. We explore the thermal conductivity of this material and find it to be much higher than that of molecular C 60 , which is a consequence of the in-plane covalent bonding. Furthermore, imaging few-layer graphullerene flakes using transmission electron microscopy and near-field nano-photoluminescence spectroscopy reveals the existence of moiré-like superlattices 3 . More broadly, the synthesis of extended carbon structures by polymerization of molecular precursors charts a clear path to the systematic design of materials for the construction of two-dimensional heterostructures with tunable optoelectronic properties., (© 2023. The Author(s), under exclusive licence to Springer Nature Limited.)

Expanded helicenes are an emerging class of helical nanocarbons composed of alternating linear and angularly fused rings, which give rise to an internal cavity and a large diameter. The latter is expected to impart exceptional chiroptical properties, but low enantiomerization free energy barriers (Δ G ‡ e that is high enough (29.2 ± 0.1 kcal/mol at 100 °C in G ‡ e . The expanded [23]-helicene, which is 7 rings longer than any known single carbohelicene and among the longest known all-carbon ladder oligomers, exhibits a Δ G ‡ e that is high enough (29.2 ± 0.1 kcal/mol at 100 °C in o -DCB) to halt enantiomerization at ambient temperature. This enabled the isolation of enantiopure samples displaying circular dichroism dissymmetry factors of ±0.056 at 428 nm, which are ≥1.7× larger than values for previously reported classical and expanded helicenes. Computational investigations suggest that this improved performance is the result of both the increased diameter and length of the [23]-helicene, providing guiding design principles for high dissymmetry molecular materials.

The synthesis of an antiaromatic tetraoxa[8]circulene annulated with four perylene diimides (PDI), giving a dynamic non-planar π-conjugated system, is described. The molecule contains 32 aromatic rings surrounding one formally antiaromatic planarized cyclooctatetraene (COT). The intense absorption (ϵ=3.35×10 5  M -1  cm -1 in CH 2 Cl 2 ) and emission bands are assigned to internal charge-transfer transitions in the combined PDI-circulene π-system. The spectroscopic data is supported by density functional theory calculations, and nuclear independent chemical shift calculation indicate that the antiaromatic COT has increased aromaticity in the reduced state. Electrochemical studies show that the compound can reversibly reach the tetra- and octa-anionic states by reduction of the four PDI units, and the deca-anionic state by reduction of the central COT ring. The material functions effectively in bulk hetero junction solar cells as a non-fullerene acceptor, reaching a power conversion efficiency of 6.4 %., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The formation of carbon-carbon bonds with transition metal reagents serves as a cornerstone of organic synthesis. Here, we show that the reactivity of an otherwise kinetically inert transition metal complex can be induced by an external electric field to affect a coupling reaction. These results highlight the importance of electric field effects in reaction chemistry and offers a new strategy to modulate organometallic reactivity.

Here we show the access to single-handed helicene nanoribbons by utilizing a [6]helicene building block to induce diastereoselective, photochemical formation of [5]helicene units. Specifically, we have synthesized nanoribbons P1 and P2 with different ratios of [6]helicene "sergeants" to [5]helicene "soldiers", which on average consist of between ∼50 and 60 ortho -annulated benzene rings. These are the longest, optically active helicene backbones that have been prepared to date. The chiroptic properties of P1 and P2 reveal the transfer of stereochemical information from "sergeants" to "soldiers". To gain further insight into the stereo-information relay, we apply the same molecular design to discrete, model oligomers 1 - 5 and confirm that they also preferentially adopt homochiral geometries.

Singlet fission occurs only in a limited number of molecules, and expanding the molecular toolbox is necessary for progress. Here, we apply the molecular contortion strategy to tune singlet and triplet energies and observe changes in the excited-state dynamics that are consistent with singlet fission playing a role in thin films of contorted perylene. Perylene is a prototypical molecular chromophore, which does not undergo singlet fission in its planar form from its S 1 state. The tuning of the energetics that control singlet fission through molecular contortion can be applied to a large repertoire of established molecular chromophores.

Reversed conductance decay describes increasing conductance of a molecular chain series with increasing chain length. Realizing reversed conductance decay is an important step toward making long and highly conducting molecular wires. Recent work has shown that one-dimensional topological insulators (1D TIs) can exhibit reversed conductance decay due to their nontrivial edge states. The Su-Schrieffer-Heeger (SSH) model for 1D TIs relates to the electronic structure of these isolated molecules but not their electron transport properties as single-molecule junctions. Herein, we use a tight-binding approach to demonstrate that polyacetylene and other diradicaloid 1D TIs show a reversed conductance decay at the short chain limit. We explain these conductance trends by analyzing the impact of the edge states in these 1D systems on the single-molecule junction transmission. Additionally, we discuss how the self-energy from the electrode-molecule coupling and the on-site energy of the edge sites can be tuned to create longer wires with reversed conductance decays.

We report a reliable way to manipulate the dynamic, axial chirality in perylene diimide (PDI)-based twistacenes. Specifically, we reveal how chiral substituents on the imide position induce the helicity in a series of PDI-based twistacenes. We demonstrate that this remote chirality is able to control the helicity of flexible [4]helicene subunits by UV-vis, CD spectroscopy, X-ray crystallography, and TDDFT calculations. Furthermore, we have discovered that both the chiral substituent and the solvent each has a strong impact on the sign and intensity of the CD signals, highlighting the control of the dynamic helicity in this flexible system. DFT calculations suggest that the steric interaction of the chiral substituents is the important factor in how well a particular group is at inducing a preferred helicity.

The electric fields created at solid-liquid interfaces are important in heterogeneous catalysis. Here we describe the Ullmann coupling of aryl iodides on rough gold surfaces, which we monitor in situ using the scanning tunneling microscope-based break junction (STM-BJ) and ex situ using mass spectrometry and fluorescence spectroscopy. We find that this Ullmann coupling reaction occurs only on rough gold surfaces in polar solvents, the latter of which implicates interfacial electric fields. These experimental observations are supported by density functional theory calculations that elucidate the roles of surface roughness and local electric fields on the reaction. More broadly, this touchstone study offers a facile method to access and probe in real time an increasingly prominent yet incompletely understood mode of catalysis., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Single-molecule topological insulators are promising candidates as conducting wires over nanometre length scales. A key advantage is their ability to exhibit quasi-metallic transport, in contrast to conjugated molecular wires which typically exhibit a low conductance that decays as the wire length increases. Here, we study a family of oligophenylene-bridged bis(triarylamines) with tunable and stable mono- or di-radicaloid character. These wires can undergo one- and two-electron chemical oxidations to the corresponding mono-cation and di-cation, respectively. We show that the oxidized wires exhibit reversed conductance decay with increasing length, consistent with the expectation for Su-Schrieffer-Heeger-type one-dimensional topological insulators. The 2.6-nm-long di-cation reported here displays a conductance greater than 0.1G 0 , where G 0 is the conductance quantum, a factor of 5,400 greater than the neutral form. The observed conductance-length relationship is similar between the mono-cation and di-cation series. Density functional theory calculations elucidate how the frontier orbitals and delocalization of radicals facilitate the observed non-classical quasi-metallic behaviour., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

We report here an iterative synthesis of long helical perylene diimide ( hPDI[ n ] ) nanoribbons with a length up to 16 fused benzene rings. These contorted, ladder-type conjugated, and atomically precise nanoribbons show great potential as organic fast-charging and long-lifetime battery cathodes. By tuning the length of the hPDI[ n ] oligomers, we can simultaneously modulate the electrical conductivity and ionic diffusivity of the material. The length of the ladders adjusts both the conjugation for electron transport and the contortion for lithium-ion transport. The longest oligomer, hPDI[6] , when fabricated as the cathode in lithium batteries, features both high electrical conductivity and high ionic diffusivity. This electrode material exhibits a high power density and can be charged in less than 1 min to 66% of its maximum capacity. Remarkably, this material also has exceptional cycling stability and can operate for up to 10,000 charging-discharging cycles without any appreciable capacity decay. The design principles described here chart a clear path for organic battery electrodes that are sustainable, fast-charging, and long lasting.

Semiconductors, featuring tunable electrical transport, and magnets, featuring tunable spin configurations, form the basis of many information technologies. A long-standing challenge has been to realize materials that integrate and connect these two distinct properties. Two-dimensional (2D) materials offer a platform to realize this concept, but known 2D magnetic semiconductors are electrically insulating in their magnetic phase. Here we demonstrate tunable electron transport within the magnetic phase of the 2D semiconductor CrSBr and reveal strong coupling between its magnetic order and charge transport. This provides an opportunity to characterize the layer-dependent magnetic order of CrSBr down to the monolayer via magnetotransport. Exploiting the sensitivity of magnetoresistance to magnetic order, we uncover a second regime characterized by coupling between charge carriers and magnetic defects. The magnetoresistance within this regime can be dynamically and reversibly tuned by varying the carrier concentration using an electrostatic gate, providing a mechanism for controlling charge transport in 2D magnets., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

2D materials can host long-range magnetic order in the presence of underlying magnetic anisotropy. The ability to realize the full potential of 2D magnets necessitates systematic investigation of the role of individual atomic layers and nanoscale inhomogeneity (i.e., strain) on the emergence of stable magnetic phases. Here, spatially dependent magnetism in few-layer CrSBr is revealed using magnetic force microscopy (MFM) and Monte Carlo-based simulations. Nanoscale visualization of the magnetic sheet susceptibility is extracted from MFM data and force-distance curves, revealing a characteristic onset of both intra- and interlayer magnetic correlations as a function of temperature and layer-thickness. These results demonstrate that the presence of a single uncompensated layer in odd-layer terraces significantly reduces the stability of the low-temperature antiferromagnetic (AFM) phase and gives rise to multiple coexisting magnetic ground states at temperatures close to the bulk Néel temperature (T N ). Furthermore, the AFM phase can be reliably suppressed using modest fields (≈16 mT) from the MFM probe, behaving as a nanoscale magnetic switch. This prototypical study of few-layer CrSBr demonstrates the critical role of layer parity on field-tunable 2D magnetism and validates MFM for use in nanomagnetometry of 2D materials (despite the ubiquitous absence of bulk zero-field magnetism in magnetized sheets)., (© 2022 Wiley-VCH GmbH.)

Coherent tunneling electron transport through molecular wires has been theoretically established as a temperature-independent process. Although several experimental studies have shown counter examples, robust models to describe this temperature dependence have not been thoroughly developed. Here, we demonstrate that dynamic molecular structures lead to temperature-dependent conductance within coherent tunneling regime. Using a custom-built variable-temperature scanning tunneling microscopy break-junction instrument, we find that oligo[ n ]phenylenes exhibit clear temperature-dependent conductance. Our calculations reveal that thermally activated dihedral rotations allow these molecular wires to have a higher probability of being in a planar conformation. As the tunneling occurs primarily through π-orbitals, enhanced coplanarization substantially increases the time-averaged tunneling probability. These calculations are consistent with the observation that more rotational pivot points in longer molecular wires leads to larger temperature-dependence on conductance. These findings reveal that molecular conductance within coherent and off-resonant electron transport regimes can be controlled by manipulating dynamic molecular structure.

The synthesis and bottom-up assembly of nanocellulose by microbes offers unique advantages to tune and meet key design criteria-rapid renewability, low toxicity, scalability, performance, and degradability-for multi-functional, circular economy textiles. However, development of green processing methods that meet these criteria remains a major research challenge. Here, we harness microbial biofabrication of nanocellulose and draw inspiration from ancient textile techniques to engineer sustainable biotextiles with a circular life cycle. The unique molecular self-organization of microbial nanocellulose (MC) combined with bio-phosphorylation with a lecithin treatment yields a compostable material with superior mechanical and flame-retardant properties. Specifically, treatment of MC with a lecithin-phosphocholine emulsion makes sites available to modulate cellulose cross-linking through hydroxyl, phosphate and methylene groups, increasing the interaction between cellulose chains. The resultant bioleather exhibits enhanced tensile strength and high ductility. Bio-phosphorylation with lecithin also redirects the combustion pathway from levoglucosan production towards the formation of foaming char as an insulating oxygen barrier, for outstanding flame retardance. Controlled color modulation is demonstrated with natural dyes. Life cycle impact assessment reveals that MC bioleather has up to an order of magnitude lower carbon footprint than conventional textiles, and a thousandfold reduction in the carcinogenic impact of leather production. Eliminating the use of hazardous substances, these high performance materials disrupt linear production models and strategically eliminate its toxicity and negative climate impacts, with widespread application in fashion, interiors and construction. Importantly, the biotextile approach developed in this study demonstrates the potential of biofabrication coupled with green chemistry for a circular materials economy., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The amplification of chiral absorbance and emission is a primary figure of merit for the design of chiral chromophores. However, for dyes to be practically relevant in chiroptical applications, they must also absorb and/or emit chiral light over broad wavelength ranges. We investigate the interplay between molecular symmetry and broad-band chiral absorbance in a series of [6]helicenes. We find that an asymmetric [6]helicene containing two distinct chromophores absorbs chiral light across a much wider wavelength range than the symmetric [6]helicenes investigated here. Chemically reducing the helicenes shifts the absorption edge of the ECD spectra into the near-infrared wavelength range while preserving broad chiral absorption, producing a [6]helicene that absorbs a single handedness of light across the entire visible wavelength range.

Redox-active two-dimensional polymers (RA-2DPs) are promising lithium battery organic cathode materials due to their regular porosities and high chemical stabilities. However, weak electrical conductivities inherent to the non-conjugated molecular motifs used thus far limit device performance and the practical relevance of these materials. We herein address this problem by developing a modular approach to construct π-conjugated RA-2DPs with a new polycyclic aromatic redox-active building block PDI-DA. Efficient imine-condensation between PDI-DA and two polyfunctional amine nodes followed by quantitative alkyl chain removal produced RA-2DPs TAPPy-PDI and TAPB-PDI as conjugated, porous, polycrystalline networks. In-plane conjugation and permanent porosity endow these materials with high electrical conductivity and high ion diffusion rates. As such, both RA-2DPs function as organic cathode materials with good rate performance and excellent cycling stability. Importantly, the improved design enables higher areal mass-loadings than were previously available, which drives a practical demonstration of TAPPy-PDI as the power source for a series of LED lights. Collectively, this investigation discloses viable synthetic methodologies and design principles for the realization of high-performance organic cathode materials., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The area of two-dimensional (2D) materials research would benefit greatly from the development of synthetically tunable van der Waals (vdW) materials. While the bottom-up synthesis of 2D frameworks from nanoscale building blocks holds great promise in this quest, there are many remaining hurdles, including the design of building blocks that reliably produce 2D lattices and the growth of macroscopic crystals that can be exfoliated to produce 2D materials. Here we report the regioselective synthesis of the cluster [ trans -Co 6 Se 8 (CN) 4 (CO) 2 ] 3-/4- , a "superatomic" building block designed to polymerize and assemble into a 2D cyanometalate lattice whose surfaces are chemically addressable. The resulting vdW material, [Co(py) 4 ] 2 [ trans -Co 6 Se 8 (CN) 4 (CO) 2 ], grows as bulk single crystals that can be mechanically exfoliated to produce flakes as thin as bilayers, with photolabile CO ligands on the exfoliated surface. As a proof of concept, we show that these surface CO ligands can be replaced by 4-isocyanoazobenzene under blue light irradiation. This work demonstrates that the bottom-up assembly of layered vdW materials from superatoms is a promising and versatile approach to create 2D materials with tunable physical and chemical properties.

Coating two-dimensional (2D) materials with molecules bearing tunable properties imparts their surfaces with functionalities for applications in sensing, nanoelectronics, nanofabrication, and electrochemistry. Here, we report a method for the site-selective surface functionalization of 2D superatomic Re 6 Se 8 Cl 2 monolayers. First, we activate bulk layered Re 6 Se 8 Cl 2 by intercalating lithium and then exfoliate the intercalation compound Li 2 Re 6 Se 8 Cl 2 in N -methylformamide (NMF). Heating the resulting solution eliminates LiCl to produce monolayer Re 6 Se 8 (NMF) 2- x ( x ≈ 0.4) as high-quality nanosheets. The unpaired electrons on each cluster in Re 6 Se 8 (NMF) 2- x enable covalent surface functionalization through radical-based chemistry. We demonstrate this to produce four previously unknown surface-functionalized 2D superatomic materials: Re 6 Se 8 I 2 , Re 6 Se 8 (SPh) 2 , Re 6 Se 8 (SPhNH 2 ) 2 , and Re 6 Se 8 (SC 16 H 33 ) 2 . Transmission electron microscopy, chemical analysis, and vibrational spectroscopy reveal that the in-plane structure of the 2D Re 6 Se 8 material is preserved through surface functionalization. We find that the incoming groups control the density of vacancy defects and the solubility of the 2D material. This approach will find utility in installing a broad array of chemical functionalities on the surface of 2D superatomic materials as a means to systematically tune their physical properties, chemical reactivity, and solution processability.

Perylene diimide (PDI) is a workhorse of the organic electronics community. However, the vast majority of designs that include PDI substitute the core with various functional groups to encourage intimate cofacial contacts between largely planar PDIs. Over the past several years, we have observed the counterintuitive result that contorting the planar aromatic core of PDI leads to higher performing photovoltaics, photodetectors, batteries, and other organic electronic devices. In this Perspective, we describe how different modes of contortion can be reliably installed into PDI-based molecules, oligomers, and polymers. We also describe how these different contortions modify the observed optical and electronic properties of PDI. For instance, contorting PDIs into bowls leads to high-efficiency singlet fission materials, while contorting PDIs into helicene-like structures leads to nonlinear amplification of Cotton effects, culminating in the highest g -factors so far observed for organic compounds. Finally, we show how these unique optoelectronic properties give rise to higher performance organic electronic devices. We specifically note how the three-dimensional structure of these contorted aromatic molecules is responsible for the enhancements in performance we observe. Throughout this Perspective, we highlight opportunities for continued study in this rapidly developing organic materials frontier.

We show that reaction pathways from a single superatom motif can be controlled through subtle electronic modification of the outer ligand spheres. Chevrel-type [Co 6 Se 8 L 6 ] (L = PR 3 , CO) superatoms are used to form carbene-terminated clusters, the reactivity of which can be influenced through the electronic effects of the surrounding ligands. This carbene provides new routes for ligand substitution chemistry, which is used to selectively install cyanide or pyridine ligands which were previously inaccessible in these cobalt-based clusters. The surrounding ligands also impact the ability of this carbene to create larger fused clusters of the type [Co 12 Se 16 L 10 ], providing underlying information for cluster fusion mechanisms. We use this information to develop methods of creating dimeric clusters with functionalized surface ligands with site specificity, putting new ligands in specific positions on this anisotropic core. Finally, adjusting the carbene intermediates can also be used to perturb the geometry of the [Co 6 Se 8 ] core itself, as we demonstrate with a multicarbene adduct that displays a substantially anisotropic core. These additional levels of synthetic control could prove instrumental for using superatomic clusters for many applications including catalysis, electronic devices, and creating novel extended structures.

The incorporation of nonhexagonal rings into graphene nanoribbons (GNRs) is an effective strategy for engineering localized electronic states, bandgaps, and magnetic properties. Here, we demonstrate the successful synthesis of nanoribbons having four-membered ring (cyclobutadienoid) linkages by using an on-surface synthesis approach involving direct contact transfer of coronene-type precursors followed by thermally assisted [2 + 2] cycloaddition. The resulting coronene-cyclobutadienoid nanoribbons feature a narrow 600-meV bandgap and novel electronic frontier states that can be interpreted as linear chains of effective p x and p y pseudo-atomic orbitals. We show that these states give rise to exceptional physical properties, such as a rigid indirect energy gap. This provides a previously unexplored strategy for constructing narrow gap GNRs via modification of precursor molecules whose function is to modulate the coupling between adjacent four-membered ring states.

Potassium-doped terphenyl has recently attracted attention as a potential host for high-transition-temperature superconductivity. Here, we elucidate the many-body electronic structure of recently synthesized potassium-doped terphenyl crystals. We show that this system may be understood as a set of weakly coupled one-dimensional ladders. Depending on the strength of the interladder coupling, the system may exhibit insulating spin-gapped valence-bond solid or antiferromagnetic phases, both of which upon hole doping may give rise to superconductivity. This terphenyl-based ladder material serves as a new platform for investigating the fate of ladder phases in the presence of three-dimensional coupling as well as for novel superconductivity.

The scanning tunneling microscope-based break-junction (STM-BJ) technique is the most common method used to study the electronic properties of single-molecule junctions. It relies on repeatedly forming and rupturing a Au contact in an environment of the target molecules. The probability of junction formation is typically very high (∼70-95%), prompting questions relating to how the nanoscale structure of the Au electrode before the metal point contact ruptures alters junction formation. Here we analyze conductance traces measured with the STM-BJ setup by combining correlation analysis and multiple machine learning tools, including gradient-boosted trees and neural networks. We show that two key features describing the Au-Au contact prior to rupture determine the extent of contact relaxation (snapback) and the probability of junction formation. Importantly, our data strongly indicate that molecular junctions are formed prior to the rupture of the Au-Au contact, explaining the high probability of junction formation observed in room-temperature solution measurements.