Peri-Alkylated Terrylenes and Ternaphthalenes Building-Blocks Towards Multi-Edge Nanographenes.

Since its first synthesis by Clar in 1948, terrylene - a fully connected ternaphthalene oligomer via naphthalene's peri-positions - has gained special focus within the rylene family, drawing interest for its unique chemical, structural, optoelectronic and single photon emission properties. In this study, we introduce a novel synthetic pathway that enhances the solubility of terrylene derivatives through complete peri-alkylation, while also facilitating extensions at the bay-positions. This approach not only broadens the scope of terrylene's chemical versatility but also opens new avenues for developing solution processable novel multi-edge nanographenes and tailoring electronic energy levels through topological edge structures. Our findings include a comprehensive structural and spectroscopic characterization along with transient absorption spectroscopy and photophysics of both the synthesized peri-alkylated terrylene and its phenylene-fused derivative.

Measuring the Capacitance of Carbon in Ionic Liquids: From Graphite to Graphene.

The physical electrochemistry of the carbon/ionic liquids interface underpins the processes occurring in a vast range of applications spanning electrochemical energy storage, iontronic devices, and lubrication. Elucidating the charge storage mechanisms at the carbon/electrolyte interface will lead to a better understanding of the operational principles of such systems. Herein, we probe the charge stored at the electrochemical double layer formed between model carbon systems, ranging from single-layer graphene to graphite and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-TFSI). The effect of the number of graphene layers on the overall capacitance of the interface is investigated. We demonstrate that in pure EMIM-TFSI and at moderate potential biases, the electronic properties of graphene and graphite govern the overall capacitance of the interface, while the electrolyte contribution to the latter is less significant. In mixtures of EMIM-TFSI with solvents of varying relative permittivity, the complex interplay between electrolyte ions and solvent molecules is shown to influence the charge stored at the interface, which under certain conditions overcomes the effects of relative permittivity. This work provides additional experimental insights into the continuously advancing topic of electrochemical double-layer structure at the interface between room temperature ionic liquids and carbon materials.

Synthesis and photoinduced behavior of DPP-anchored nitronyl nitroxides: a multifaceted approach.

Understanding and controlling spin dynamics in organic dyes is of significant scientific and technological interest. The investigation of 2,5-dihydropyrrolo[4,3-c]pyrrolo-1,4-dione derivatives (DPPs), one of the most widely used dyes in many fields, has so far been limited to closed-shell molecules. We present a comprehensive joint experimental and computational study of DPP derivatives covalently linked to two nitronyl nitroxide radicals (DPPTh-NN2). Synthesis, single crystal X-ray diffraction study, photophysical properties, magnetic properties established using steady-state and pulse EPR, fast spin dynamics, and computational modelling using density functional theory and ab initio methods of electronic structure and spectroscopic properties of DPPTh-NN2 are presented. The single-crystal X-ray diffraction analysis of DPPTh-NN2 and computational modeling of its electronic structure suggest that effective conjugation along the backbone leads to noticeable spin-polarization transfer. Calculations using ab initio methods predict a weak exchange interaction of radical centers through a singlet ground state of DPPTh with a small singlet-triplet splitting (ΔEST) of about 25 cm-1 (∼0.07 kcal mol-1). In turn, a strong ferromagnetic exchange interaction between the triplet state of DPPTh chromophore and nitronyl nitroxides (with J ∼ 250 cm-1) was predicted.

Fabrication of angstrom-scale two-dimensional channels for mass transport.

Fluidic channels at atomic scales regulate cellular trafficking and molecular filtration across membranes, and thus play crucial roles in the functioning of living systems. However, constructing synthetic channels experimentally at these scales has been a significant challenge due to the limitations in nanofabrication techniques and the surface roughness of the commonly used materials. Angstrom (Å)-scale slit-like channels overcome such challenges as these are made with precise control over their dimensions and can be used to study the fluidic properties of gases, ions and water at unprecedented scales. Here we provide a detailed fabrication method of the two-dimensional Å-scale channel devices that can be assembled to contain a desired number of channels, a single channel or up to hundreds of channels, made with atomic-scale precision using layered crystals. The procedure includes the fabrication of the substrate, flake, spacer layer, flake transfers, van der Waals assembly and postprocessing. We further explain how to perform molecular transport measurements with the Å-channels to directly probe the intriguing and anomalous phenomena that help shed light on the physics governing ultra-confined transport. The procedure requires a total of 1-2 weeks for the fabrication of the two-dimensional channel device and is suitable for users with prior experience in clean room working environments and nanofabrication.

Liquid-activated quantum emission from pristine hexagonal boron nitride for nanofluidic sensing.

Liquids confined down to the atomic scale can show radically new properties. However, only indirect and ensemble measurements operate in such extreme confinement, calling for novel optical approaches that enable direct imaging at the molecular level. Here we harness fluorescence originating from single-photon emitters at the surface of hexagonal boron nitride for molecular imaging and sensing in nanometrically confined liquids. The emission originates from the chemisorption of organic solvent molecules onto native surface defects, revealing single-molecule dynamics at the interface through the spatially correlated activation of neighbouring defects. Emitter spectra further offer a direct readout of the local dielectric properties, unveiling increasing dielectric order under nanometre-scale confinement. Liquid-activated native hexagonal boron nitride defects bridge the gap between solid-state nanophotonics and nanofluidics, opening new avenues for nanoscale sensing and optofluidics.

Beyond steric selectivity of ions using ångström-scale capillaries.

Ion-selective channels play a key role in physiological processes and are used in many technologies. Although biological channels can efficiently separate same-charge ions with similar hydration shells, it remains a challenge to mimic such exquisite selectivity using artificial solid-state channels. Although there are several nanoporous membranes that show high selectivity with respect to certain ions, the underlying mechanisms are based on the hydrated ion size and/or charge. There is a need to rationalize the design of artificial channels to make them capable of selecting between similar-sized same-charge ions, which, in turn, requires an understanding of why and how such selectivity can occur. Here we study ångström-scale artificial channels made by van der Waals assembly, which are comparable in size with typical ions and carry little residual charge on the channel walls. This allows us to exclude the first-order effects of steric- and Coulomb-based exclusion. We show that the studied two-dimensional ångström-scale capillaries can distinguish between same-charge ions with similar hydrated diameters. The selectivity is attributed to different positions occupied by ions within the layered structure of nanoconfined water, which depend on the ion-core size and differ for anions and cations. The revealed mechanism points at the possibilities of ion separation beyond simple steric sieving.

Anion Intercalation into Graphite Drives Surface Wetting.

The unique layered structure of graphite with its tunable interlayer distance establishes almost ideal conditions for the accommodation of ions into its structure. The smooth and chemically inert nature of the graphite surface also means that it is an ideal substrate for electrowetting. Here, we combine these two unique properties of this material by demonstrating the significant effect of anion intercalation on the electrowetting response of graphitic surfaces in contact with concentrated aqueous and organic electrolytes as well as ionic liquids. The structural changes during intercalation/deintercalation were probed using in situ Raman spectroscopy, and the results were used to provide insights into the influence of intercalation staging on the rate and reversibility of electrowetting. We show, by tuning the size of the intercalant and the stage of intercalation, that a fully reversible electrowetting response can be attained. The approach is extended to the development of biphasic (oil/water) systems that exhibit a fully reproducible electrowetting response with a near-zero voltage threshold and unprecedented contact angle variations of more than 120° within a potential window of less than 2 V.

Enhanced nanofluidic transport in activated carbon nanoconduits.

Carbon has emerged as a unique material in nanofluidics, with reports of fast water transport, molecular ion separation and efficient osmotic energy conversion. Many of these phenomena still await proper rationalization due to the lack of fundamental understanding of nanoscale ionic transport, which can only be achieved in controlled environments. Here we develop the fabrication of 'activated' two-dimensional carbon nanochannels. Compared with nanoconduits with 'pristine' graphite walls, this enables the investigation of nanoscale ionic transport in great detail. We show that activated carbon nanochannels outperform pristine channels by orders of magnitude in terms of surface electrification, ionic conductance, streaming current and (epi-)osmotic currents. A detailed theoretical framework enables us to attribute the enhanced ionic transport across activated carbon nanochannels to an optimal combination of high surface charge and low friction. Furthermore, this demonstrates the unique potential of activated carbon for energy harvesting from salinity gradients with single-pore power density across activated carbon nanochannels, reaching hundreds of kilowatts per square metre, surpassing alternative nanomaterials.

Water friction in nanofluidic channels made from two-dimensional crystals.

Membrane-based applications such as osmotic power generation, desalination and molecular separation would benefit from decreasing water friction in nanoscale channels. However, mechanisms that allow fast water flows are not fully understood yet. Here we report angstrom-scale capillaries made from atomically flat crystals and study the effect of confining walls' material on water friction. A massive difference is observed between channels made from isostructural graphite and hexagonal boron nitride, which is attributed to different electrostatic and chemical interactions at the solid-liquid interface. Using precision microgravimetry and ion streaming measurements, we evaluate the slip length, a measure of water friction, and investigate its possible links with electrical conductivity, wettability, surface charge and polarity of the confining walls. We also show that water friction can be controlled using hybrid capillaries with different slip lengths at opposing walls. The reported advances extend nanofluidics' toolkit for designing smart membranes and mimicking manifold machinery of biological channels.

Hydrocarbon contamination in angström-scale channels.

Nonspecific molecular adsorption such as airborne contamination occurs on most surfaces including those of 2D materials and alters their properties. While surface contamination is studied using a plethora of techniques, the effect of contamination on confined systems such as nanochannels/pores leading to their clogging is still lacking. We report a systematic investigation of hydrocarbon adsorption in angstrom (Å) slit channels of varying heights. Hexane is chosen to mimic the hydrocarbon contamination and the clogging of the Å-channels is evaluated via a helium gas flow measurement. The level of hexane adsorption, in other words, the degree of clogging depends on the size difference between the channels and hexane. A dynamic transition of the clogging and revival process is shown in sub-2 nm thin channels. Long-term storage and stability of our Å-channels are demonstrated here for up to three years, alleviating the contamination and unclogging the channels using thermal treatment. This study highlights the importance of the nanochannels' stability and demonstrates the self-cleansing nature of sub-2 nm thin channels enabling a robust platform for molecular transport and separation studies. We provide a method to assess the cleanliness of nanoporous membranes, which is vital for the practical applications of nanofluidics in various fields such as molecular sensing, separation and power generation.

Translocation of DNA through Ultrathin Nanoslits.

2D nanoslit devices, where two crystals with atomically flat surfaces are separated by only a few nanometers, have attracted considerable attention because their tunable control over the confinement allows for the discovery of unusual transport behavior of gas, water, and ions. Here, the passage of double-stranded DNA molecules is studied through nanoslits fabricated from exfoliated 2D materials, such as graphene or hexagonal boron nitride, and the DNA polymer behavior is examined in this tight confinement. Two types of events are observed in the ionic current: long current blockades that signal DNA translocation and short spikes where DNA enters the slits but withdraws. DNA translocation events exhibit three distinct phases in their current-blockade traces-loading, translation, and exit. Coarse-grained molecular dynamics simulation allows the different polymer configurations of these phases to be identified. DNA molecules, including folds and knots in their polymer structure, are observed to slide through the slits with near-uniform velocity without noticeable frictional interactions of DNA with the confining graphene surfaces. It is anticipated that this new class of 2D-nanoslit devices will provide unique ways to study polymer physics and enable lab-on-a-chip biotechnology.

Gas flow through atomic-scale apertures.

Gas flows are often analyzed with the theoretical descriptions formulated over a century ago and constantly challenged by the emerging architectures of narrow channels, slits, and apertures. Here, we report atomic-scale defects in two-dimensional (2D) materials as apertures for gas flows at the ultimate quasi-0D atomic limit. We establish that pristine monolayer tungsten disulfide (WS2) membranes act as atomically thin barriers to gas transport. Atomic vacancies from missing tungsten (W) sites are made in freestanding (WS2) monolayers by focused ion beam irradiation and characterized using aberration-corrected transmission electron microscopy. WS2 monolayers with atomic apertures are mechanically sturdy and showed fast helium flow. We propose a simple yet robust method for confirming the formation of atomic apertures over large areas using gas flows, an essential step for pursuing their prospective applications in various domains including molecular separation, single quantum emitters, sensing and monitoring of gases at ultralow concentrations.

On-surface Synthesis of a Chiral Graphene Nanoribbon with Mixed Edge Structure.

Chiral graphene nanoribbons represent an important class of graphene nanomaterials with varying combinations of armchair and zigzag edges conferring them unique structure-dependent electronic properties. Here, we describe the on-surface synthesis of an unprecedented cove-edge chiral GNR with a benzo-fused backbone on a Au(111) surface using 2,6-dibromo-1,5-diphenylnaphthalene as precursor. The initial precursor self-assembly and the formation of the chiral GNRs upon annealing are revealed, along with a relatively small electronic bandgap of approximately 1.6 eV, by scanning tunnelling microscopy and spectroscopy.

On-Surface Dehydro-Diels-Alder Reaction of Dibromo-bis(phenylethynyl)benzene.

On-surface synthesis under ultrahigh vacuum conditions is a powerful tool to achieve molecular structures that cannot be accessed via traditional wet chemistry. Nevertheless, only a very limited number of chemical reactions out of the wide variety known from solution chemistry have been reported to proceed readily on atomically flat substrates. Cycloadditions are a class of reactions that are particularly important in the synthesis of sp2-hybridized carbon-based nanostructures. Here, we report on a specific type of [4 + 2] cycloaddition, namely, a dehydro-Diels-Alder (DDA) reaction, performed between bis(phenylethynyl)-benzene precursors on Au(111). Unlike a Diels-Alder reaction, DDA exploits ethynyl groups to achieve the formation of an extra six-membered ring. Despite its extensive use in solution chemistry for more than a century, this reaction has never been reported to occur on surfaces. The specific choice of our precursor molecule has led to the successful synthesis of benzo- and naphtho-fused tetracene and heptacene products bearing styryl groups, as confirmed by scanning tunneling microscopy and noncontact atomic force microscopy. The two products arise from dimerization and trimerization of the precursor molecules, respectively, and their observation opens perspectives to use DDA reactions as a novel on-surface synthesis tool.

On-Surface Synthesis of a Nonplanar Porous Nanographene.

On-surface synthesis provides an effective approach toward the formation of graphene nanostructures that are difficult to achieve via traditional solution chemistry. Here, we report on the design and synthesis of a nonplanar porous nanographene with 78 sp 2 carbon atoms, namely C78. Through a highly selective oxidative cyclodehydrogenation of 2,3,6,7,10,11-hexa(naphthalen-1-yl)triphenylene (2), propeller nanographene precursor 1 was synthesized in solution. Interestingly, although 1 could not be cyclized further in solution, porous nanographene C78 was successfully achieved from 1 by on-surface assisted cyclodehydrogenation on Au(111). The structure and electronic properties of C78 have been investigated by means of scanning tunneling microscopy, noncontact atomic force microscopy, and scanning tunneling spectroscopy, complemented by computational investigations. Our results provide perspectives for the on-surface synthesis of porous graphene nanostructures, offering a promising strategy for the engineering of graphene materials with tailor-made properties.

Capacitance of Basal Plane and Edge-Oriented Highly Ordered Pyrolytic Graphite: Specific Ion Effects.

Carbon materials are ubiquitous in energy storage; however, many of the fundamental electrochemical properties of carbons are still not fully understood. In this work, we studied the capacitance of highly ordered pyrolytic graphite (HOPG), with the aim of investigating specific ion effects seen in the capacitance of the basal plane and edge-oriented planes of the material. A series of alkali metal cations, from Li+, Na+, K+, Rb+, and Cs+ with chloride as the counterion, were used at a fixed electrolyte concentration. The basal plane capacitance at a fixed potential relative to the potential of zero charge was found to increase from 4.72 to 9.39 µF cm-2 proceeding down Group 1. In contrast, the edge-orientated samples display capacitance ca. 100 times higher than those of the basal plane, attributed to pseudocapacitance processes associated with the presence of oxygen groups and largely independent of cation identity. This work improves understanding of capacitive properties of carbonaceous materials, leading to their continued development for use in energy storage.

Magnetic edge states and coherent manipulation of graphene nanoribbons.

Graphene, a single-layer network of carbon atoms, has outstanding electrical and mechanical properties 1 . Graphene ribbons with nanometre-scale widths2,3 (nanoribbons) should exhibit half-metallicity 4 and quantum confinement. Magnetic edges in graphene nanoribbons5,6 have been studied extensively from a theoretical standpoint because their coherent manipulation would be a milestone for spintronic 7 and quantum computing devices 8 . However, experimental investigations have been hampered because nanoribbon edges cannot be produced with atomic precision and the graphene terminations that have been proposed are chemically unstable 9 . Here we address both of these problems, by using molecular graphene nanoribbons functionalized with stable spin-bearing radical groups. We observe the predicted delocalized magnetic edge states and test theoretical models of the spin dynamics and spin-environment interactions. Comparison with a non-graphitized reference material enables us to clearly identify the characteristic behaviour of the radical-functionalized graphene nanoribbons. We quantify the parameters of spin-orbit coupling, define the interaction patterns and determine the spin decoherence channels. Even without any optimization, the spin coherence time is in the range of microseconds at room temperature, and we perform quantum inversion operations between edge and radical spins. Our approach provides a way of testing the theory of magnetism in graphene nanoribbons experimentally. The coherence times that we observe open up encouraging prospects for the use of magnetic nanoribbons in quantum spintronic devices.

Publisher Correction: Magnetic edge states and coherent manipulation of graphene nanoribbons.

In Fig. 1 of this Letter, there should have been two nitrogen (N) atoms at the 1,3-positions of all the blue chemical structures (next to the oxygen atoms), rather than one at the 2-position. The figure has been corrected online, and the original incorrect figure is shown as Supplementary Information to the accompanying Amendment.

Molecular Ordering of Dithieno[2,3-d;2',3'-d]benzo[2,1-b:3,4-b']dithiophenes for Field-Effect Transistors.

Four derivatives of dithieno[2,3-d;2',3'-d']benzo[1,2-b;3,4-b']dithiophene (DTmBDT) have been synthesized to investigate the correlation between molecular structure, thin-film organization, and charge-carrier transport. Phenyl or thiophene end-capped derivatives at alpha positions of the outer thiophenes of DTmBDT present vastly different optoelectronic properties in comparison with bay-position alkyl-chain-substituted DTmBDT, which was additionally confirmed by density functional theory simulations. The film morphology of the derivatives strongly depends on alkyl substituents, aromatic end-caps, and substrate temperature. Field-effect transistors based on DTmBDT derivatives with bay-substituted alkyl chains show the best performance within this studied series with a hole mobility up to 0.75 cm2/V s. Attachment of aromatic end-caps disturbs the ordering, limiting the charge-carrier transport. Higher substrate temperature during deposition of the DTmBDT derivatives with aromatic end-caps results in larger domains and improved the transistor mobilities but not beyond the alkylated DTmBDT.

Edge Functionalization of Structurally Defined Graphene Nanoribbons for Modulating the Self-Assembled Structures.

Edge functionalization of bottom-up synthesized graphene nanoribbons (GNRs) with anthraquinone and naphthalene/perylene monoimide units has been achieved through a Suzuki coupling of polyphenylene precursors bearing bromo groups, prior to the intramolecular oxidative cyclo-dehydrogenation. High efficiency of the substitution has been validated by MALDI-TOF MS analysis of the functionalized precursors and FT-IR, Raman, and XPS analyses of the resulting GNRs. Moreover, AFM measurements demonstrated the modulation of the self-assembling behavior of the edge-functionalized GNRs, revealing that GNR-PMI formed an intriguing rectangular network. This result suggests the possibility of programming the supramolecular architecture of GNRs by tuning the functional units.