Tailoring giant quantum transport anisotropy in nanoporous graphenes under electrostatic disorder.

During the last 15 years bottom-up on-surface synthesis has been demonstrated as an efficient way to synthesize carbon nanostructures with atomic precision, opening the door to unprecedented electronic control at the nanoscale. Nanoporous graphenes (NPGs) fabricated as two-dimensional arrays of graphene nanoribbons (GNRs) represent one of the key recent breakthroughs in the field. NPGs interestingly display in-plane transport anisotropy of charge carriers, and such anisotropy was shown to be tunable by modulating quantum interference. Herein, using large-scale quantum transport simulations, we show that electrical anisotropy in NPGs is not only resilient to disorder but can further be massively enhanced by its presence. This outcome paves the way to systematic engineering of quantum transport in NPGs as a novel concept for efficient quantum devices and architectures.

Mechanistic Insights into Electronic Current Flow through Quinone Devices.

Molecular switches based on functionalized graphene nanoribbons (GNRs) are of great interest in the development of nanoelectronics. In experiment, it was found that a significant difference in the conductance of an anthraquinone derivative can be achieved by altering the pH value of the environment. Building on this, in this work we investigate the underlying mechanism behind this effect and propose a general design principle for a pH based GNR-based switch. The electronic structure of the investigated systems is calculated using density functional theory and the transport properties at the quasi-stationary limit are described using nonequilibrium Green's function and the Landauer formalism. This approach enables the examination of the local and the global transport through the system. The electrons are shown to flow along the edges of the GNRs. The central carbonyl groups allow for tunable transport through control of the oxidation state via the pH environment. Finally, we also test different types of GNRs (zigzag vs. armchair) to determine which platform provides the best transport switchability.

Emergent Spin Frustration in Neutral Mixed-Valence 2D Conjugated Polymers: A Potential Quantum Materials Platform.

Two-dimensional conjugated polymers (2DCPs)─organic 2D materials composed of arrays of carbon sp2 centers connected by π-conjugated linkers─are attracting increasing attention due to their potential applications in device technologies. This interest stems from the ability of 2DCPs to host a range of correlated electronic and magnetic states (e.g., Mott insulators). Substitution of all carbon sp2 centers in 2DCPs by nitrogen or boron results in diamagnetic insulating states. Partial substitution of C sp2 centers by B or N atoms has not yet been considered for extended 2DCPs but has been extensively studied in the analogous neutral mixed-valence molecular systems. Here, we employ accurate first-principles calculations to predict the electronic and magnetic properties of a new class of hexagonally connected neutral mixed-valence 2DCPs in which every other C sp2 nodal center is substituted by either a N or B atom. We show that these neutral mixed-valence 2DCPs significantly energetically favor a state with emergent superexchange-mediated antiferromagnetic (AFM) interactions between C-based spin-1/2 centers on a triangular sublattice. These AFM interactions are surprisingly strong and comparable to those in the parent compounds of cuprate superconductors. The rigid and covalently linked symmetric triangular AFM lattice in these materials thus provides a highly promising and robust basis for 2D spin frustration. As such, extended mixed-valence 2DCPs are a highly attractive platform for the future bottom-up realization of a new class of all-organic quantum materials, which could host exotic correlated electronic states (e.g., unusual magnetic ordering, quantum spin liquids).

Unveiling the Multiradical Character of the Biphenylene Network and Its Anisotropic Charge Transport.

Recent progress in the on-surface synthesis and characterization of nanomaterials is facilitating the realization of new carbon allotropes, such as nanoporous graphenes, graphynes, and 2D π-conjugated polymers. One of the latest examples is the biphenylene network (BPN), which was recently fabricated on gold and characterized with atomic precision. This gapless 2D organic material presents uncommon metallic conduction, which could help develop innovative carbon-based electronics. Here, using first principles calculations and quantum transport simulations, we provide new insights into some fundamental properties of BPN, which are key for its further technological exploitation. We predict that BPN hosts an unprecedented spin-polarized multiradical ground state, which has important implications for the chemical reactivity of the 2D material under practical use conditions. The associated electronic band gap is highly sensitive to perturbations, as seen in finite temperature (300 K) molecular dynamics simulations, but the multiradical character remains stable. Furthermore, BPN is found to host in-plane anisotropic (spin-polarized) electrical transport, rooted in its intrinsic structural features, which suggests potential device functionality of interest for both nanoelectronics and spintronics.

Acetylene-Mediated Electron Transport in Nanostructured Graphene and Hexagonal Boron Nitride.

The discovery of graphene has catalyzed the search for other 2D carbon allotropes, such as graphynes, graphdiynes, and 2D π-conjugated polymers, which have been theoretically predicted or experimentally synthesized during the past decade. These materials exhibit a conductive nature bound to their π-conjugated sp2 electronic system. Some cases include sp-hybridized moieties in their nanostructure, such as acetylenes in graphynes; however, these act merely as electronic couplers between the conducting π-orbitals of sp2 centers. Herein, via first-principles calculations and quantum transport simulations, we demonstrate the existence of an acetylene-meditated transport mechanism entirely hosted by sp-hybridized orbitals. For that we propose a series of nanostructured 2D materials featuring linear arrangements of closely packed acetylene units which function as sp-nanowires. Because of the very distinct nature of this unique transport mechanism, it appears to be highly complementary with π-conjugation, thus potentially becoming a key tool for future carbon nanoelectronics.

Controlling pairing of π-conjugated electrons in 2D covalent organic radical frameworks via in-plane strain.

Controlling the electronic states of molecules is a fundamental challenge for future sub-nanoscale device technologies. π-conjugated bi-radicals are very attractive systems in this respect as they possess two energetically close, but optically and magnetically distinct, electronic states: the open-shell antiferromagnetic/paramagnetic and the closed-shell quinoidal diamagnetic states. While it has been shown that it is possible to statically induce one electronic ground state or the other by chemical design, the external dynamical control of these states in a rapid and reproducible manner still awaits experimental realization. Here, via quantum chemical calculations, we demonstrate that in-plane uniaxial strain of 2D covalently linked arrays of radical units leads to smooth and reversible conformational changes at the molecular scale that, in turn, induce robust transitions between the two kinds of electronic distributions. Our results pave a general route towards the external control, and thus technological exploitation, of molecular-scale electronic states in organic 2D materials.

Conformational control over π-conjugated electron pairing in 1D organic polymers.

During the past decades π-conjugated bi-radicals have attracted increasing attention, due to the existence of two close-in-energy resonant electronic configurations with very distinct characteristics: the open-shell bi-radical and the closed-shell quinoidal. The chemical design of the bi-radical structure has been shown to be very effective to shift the balance towards one, or the other, electronic distribution. Some reports have experimentally studied the analogous 1D oligomers and polymers, however, only the open-shell multi-radical configuration has been detected, and it is yet not very clear which structural and chemical parameters are relevant in such extended systems. In this work, via first principles quantum chemical simulations, we study a series of π-conjugated 1D polymers based on triarylmethyl radicals with different chemical functionalization. We find that dihedral angles of the aryl rings connecting the radical centres are the key conformational parameter determining the electronic balance. This provides a simple recipe to use chemical functionalization of aryl rings as a tool to shift the system towards either the electron paired or unpaired configurations. Additionally, we find such conformational control is also effective under the effect of thermal fluctuations, which highlights its potential technological applicability.

Neutral Organic Radical Formation by Chemisorption on Metal Surfaces.

Organic radical monolayers (r-MLs) bonded to metal surfaces are potential materials for the development of molecular (spin)electronics. Typically, stable radicals bearing surface anchoring groups are used to generate r-MLs. Following a recent theoretical proposal based on a model system, we report the first experimental realization of a metal surface-induced r-ML, where a rationally chosen closed-shell precursor 3,5-dichloro-4-[bis(2,4,6-trichlorophenyl)methylen]cyclohexa-2,5-dien-1-one (1) transforms into a stable neutral open-shell species (1•) via chemisorption on the Ag(111) surface. X-ray photoelectron spectroscopy reveals that the >C═O group of 1 reacts with the surface, forming a C-O-Ag linkage that induces an electronic rearrangement that transforms 1 to 1•. We further show that surface reactivity is an important factor in this process whereby Au(111) is inert towards 1, whereas the Cu(111) surface leads to dehalogenation reactions. The radical nature of the Ag(111)-bound monolayer was further confirmed by angle-resolved photoelectron spectroscopy and electronic structure calculations, which provide evidence of the emergence of the singly occupied molecular orbital (SOMO) of 1•.

Quantum Interference Engineering of Nanoporous Graphene for Carbon Nanocircuitry.

Bottom-up prepared carbon nanostructures appear as promising platforms for future carbon-based nanoelectronics due to their atomically precise and versatile structure. An important breakthrough is the recent preparation of nanoporous graphene (NPG) as an ordered covalent array of graphene nanoribbons (GNRs). Within NPG, the GNRs may be thought of as 1D electronic nanochannels through which electrons preferentially move, highlighting NPG's potential for carbon nanocircuitry. However, the π-conjugated bonds bridging the GNRs give rise to electronic crosstalk between the individual 1D channels, leading to spatially dispersing electronic currents. Here, we propose a chemical design of the bridges resulting in destructive quantum interference, which blocks the crosstalk between GNRs in NPG, electronically isolating them. Our multiscale calculations reveal that injected currents can remain confined within a single, 0.7 nm wide, GNR channel for distances as long as 100 nm. The concepts developed in this work thus provide an important ingredient for the quantum design of future carbon nanocircuitry.

Existence of multi-radical and closed-shell semiconducting states in post-graphene organic Dirac materials.

Post-graphene organic Dirac (PGOD) materials are ordered two-dimensional networks of triply bonded sp 2 carbon nodes spaced by π-conjugated linkers. PGOD materials are natural chemical extensions of graphene that promise to have an enhanced range of properties and applications. Experimentally realised molecules based on two PGOD nodes exhibit a bi-stable closed-shell/multi-radical character that can be understood through competing Lewis resonance forms. Here, following the same rationale, we predict that similar states should be accessible in PGOD materials, which we confirm using accurate density functional theory calculations. Although for graphene the semimetallic state is always dominant, for PGOD materials this state becomes marginally meta-stable relative to open-shell multi-radical and/or closed-shell states that are stabilised through symmetry breaking, in line with analogous molecular systems. These latter states are semiconducting, increasing the potential use of PGOD materials as highly tuneable platforms for future organic nano-electronics and spintronics.

Design of multi-functional 2D open-shell organic networks with mechanically controllable properties.

Triarylmethyls (TAMs) are prominent highly attractive open shell organic molecular building blocks for materials science, having been used in breakthrough syntheses of organic magnetic polymers and metal organic frameworks. With their radical π-conjugated nature and a proven capacity to possess high stability via suitable chemical design, TAMs display a variety of desirable characteristics which can be exploited for a wide range of applications. Due to their particular molecular and electronic structure, the spin localization in TAMs almost entirely depends on the dihedral angles of their three aryl rings with respect to the central methyl carbon atom plane, which opens up the possibility of controlling their fundamental properties by twisting the three aryl rings. Aryl ring twist angles can be tuned to a single value by specific chemical functionalisation but controlling them by external means in organic materials or devices represents a challenging task which has not yet been experimentally achieved. Herein, through rational chemical design we propose two 2D covalent organic frameworks (2D-COFs) based on specific TAM building blocks. By employing ab initio computational modeling we demonstrate that it is possible to externally manipulate the aryl ring twist angles in these 2D-linked TAM frameworks by external mechanical means. Furthermore, we show this structural manipulation allows for finely tuning the most important characteristics of these materials such as spin localization, optical electronic transitions and magnetic interactions. Due to the enormous technological potential offered by this new class of material and the fact that our work is guided by real advances in organic materials synthesis, we believe that our predictions will inspire the experimental realization of radical-2D-COFs with externally controllable characteristics.

Operative Mechanism of Hole-Assisted Negative Charge Motion in Ground States of Radical-Anion Molecular Wires.

Charge transfer/transport in molecular wires over varying distances is a subject of great interest. The feasible transport mechanisms have been generally accounted for on the basis of tunneling or superexchange charge transfer operating over small distances which progressively gives way to hopping transport over larger distances. The underlying molecular sequential steps that likely take place during hopping and the operative mechanism occurring at intermediate distances have received much less attention given the difficulty in assessing detailed molecular-level information. We describe here the operating mechanisms for unimolecular electron transfer/transport in the ground state of radical-anion mixed-valence derivatives occurring between their terminal perchlorotriphenylmethyl/ide groups through thiophene-vinylene oligomers that act as conjugated wires of increasing length up to 53 Å. The unique finding here is that the net transport of the electron in the larger molecular wires is initiated by an electron-hole dissociation intermediated by hole delocalization (conformationally assisted and thermally dependent) forming transient mobile polaronic states in the bridge that terminate by an electron-hole recombination at the other wire extreme. On the contrary, for the shorter radical-anions our results suggest that a flickering resonance mechanism which is intermediate between hopping and superexchange is the operative one. We support these mechanistic interpretations by applying the pertinent biased kinetic models of the charge/spin exchange rates determined by electron paramagnetic resonance and by molecular structural level information obtained from UV-vis and Raman spectroscopies and by quantum chemical modeling.

Looking Inside the Perchlorinated Trityl Radical/Metal Spinterface through Spectroscopy.

We report on a spectroscopic multitechnique approach to study the metal/radical spinterface formed by a perchlorinated trityl radical derivative and either gold or silver. The spectroscopic fingerprint of their paramagnetic properties could be determined by comparison with their diamagnetic precursor and by DFT calculations. Thanks to the presented approach, we could gain unprecedented insight into the radical-metal interaction and how this latter perturbs the spin polarization and consequently the magnetoelectronic properties of the radical adlayer. Knowledge of the factors influencing the spinterface is an essential tool toward the tailoring of the properties of spin-based electronic devices.

Kondo effect in a neutral and stable all organic radical single molecule break junction.

Organic radicals are neutral, purely organic molecules exhibiting an intrinsic magnetic moment due to the presence of an unpaired electron in the molecule in its ground state. This property, added to the low spin-orbit coupling and weak hyperfine interactions, make neutral organic radicals good candidates for molecular spintronics insofar as the radical character is stable in solid state electronic devices. Here we show that the paramagnetism of the polychlorotriphenylmethyl radical molecule in the form of a Kondo anomaly is preserved in two- and three-terminal solid-state devices, regardless of mechanical and electrostatic changes. Indeed, our results demonstrate that the Kondo anomaly is robust under electrodes displacement and changes of the electrostatic environment, pointing to a localized orbital in the radical as the source of magnetism. Strong support to this picture is provided by density functional calculations and measurements of the corresponding nonradical species. These results pave the way toward the use of all-organic neutral radical molecules in spintronics devices and open the door to further investigations into Kondo physics.