Differences in enantiomeric diffusion can lead to selective chiral amplification.

A fundamental question associated with chirality is how mixtures containing equal amounts of interconverting enantiomers can spontaneously convert to systems enriched in only one of them. Enantiomers typically have similar chemical properties, but can exhibit distinct reactivity under specific conditions, and these differences can be used to bias the system's composition in favor of one enantiomer. Transport properties are also expected to differ for enantiomers in chiral solvents, but the role of such differences in chiral symmetry breaking has not been clarified yet. In this work, we develop a theoretical framework to show that asymmetry in diffusion properties can trigger a spontaneous and selective symmetry breaking in mixtures of enantiomers. We derive a generic evolution equation for the enantiomeric excess in a chiral solvent. This equation shows that the relative stability of homochiral domains is dictated by the difference of diffusion coefficients of the two enantiomers. Consequently, deracemization toward a specific enantiomeric excess can be achieved when this difference is large enough. These results hold significant implications for our understanding of chiral symmetry breaking.

Gas Release as an Efficient Strategy to Tune Mechanical Properties and Thermoresponsiveness of Dynamic Molecular Crystals.

Dynamic molecular crystals combining multiple and finely tunable functionalities are attracting and an increasing attention due to their potential applications in a broad range of fields as efficient energy transducers and stimuli-responsive materials. In this context, a multicomponent organic salt, piperazinium trifluoroacetate (PZTFA), endowed with an unusual multidimensional responsive landscape is reported. Crystals of the salt undergo smooth plastic deformation under mechanical stress and thermo-induced jumping. Furthermore, via controlled crystal bending and release of trifluoroacetic acid from the lattice, which is anticipated from the design of the material, both the mechanical response and the thermoresponsive behavior are efficiently tuned while partially preserving the crystallinity of the system. In particular, mechanical deformation hampers guest release and hence the macroscopic jumping effect, while trifluoroacetic acid release stiffens the crystals. These complex adaptive responses establish a new crystal engineering strategy to gain further control over dynamic organic crystals.

Transiently delocalized states enhance hole mobility in organic molecular semiconductors.

Evidence shows that charge carriers in organic semiconductors self-localize because of dynamic disorder. Nevertheless, some organic semiconductors feature reduced mobility at increasing temperature, a hallmark for delocalized band transport. Here we present the temperature-dependent mobility in two record-mobility organic semiconductors: dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]-thiophene (DNTT) and its alkylated derivative, C8-DNTT-C8. By combining terahertz photoconductivity measurements with atomistic non-adiabatic molecular dynamics simulations, we show that while both crystals display a power-law decrease of the mobility (µ) with temperature (T) following µ ∝ T -n, the exponent n differs substantially. Modelling reveals that the differences between the two chemically similar semiconductors can be traced to the delocalization of the different states that are thermally accessible by charge carriers, which in turn depends on their specific electronic band structure. The emerging picture is that of holes surfing on a dynamic manifold of vibrationally dressed extended states with a temperature-dependent mobility that provides a sensitive fingerprint for the underlying density of states.

High-Performance Humidity Sensing in π-Conjugated Molecular Assemblies through the Engineering of Electron/Proton Transport and Device Interfaces.

The development of systems capable of responding to environmental changes, such as humidity, requires the design and assembly of highly sensitive and efficiently transducing elements. Such a challenge can be mastered only by disentangling the role played by each component of the responsive system, thus ultimately achieving high performance by optimizing the synergistic contribution of all functional elements. Here, we designed and synthesized a novel [1]benzothieno[3,2-b][1]benzothiophene derivative equipped with hydrophilic oligoethylene glycol lateral chains (OEG-BTBT) that can electrically transduce subtle changes in ambient humidity with high current ratios (>104) at low voltages (2 V), reaching state-of-the-art performance. Multiscale structural, spectroscopical, and electrical characterizations were employed to elucidate the role of each device constituent, viz., the active material's BTBT core and OEG side chains, and the device interfaces. While the BTBT molecular core promotes the self-assembly of (semi)conducting crystalline films, its OEG side chains are prone to adsorb ambient moisture. These chains act as hotspots for hydrogen bonding with atmospheric water molecules that locally dissociate when a bias voltage is applied, resulting in a mixed electronic/protonic long-range conduction throughout the film. Due to the OEG-BTBT molecules' orientation with respect to the surface and structural defects within the film, water molecules can access the humidity-sensitive sites of the SiO2 substrate surface, whose hydrophilicity can be tuned for an improved device response. The synergistic chemical engineering of materials and interfaces is thus key for designing highly sensitive humidity-responsive electrical devices whose mechanism relies on the interplay of electron and proton transport.

Temperature-induced polymorphism of a benzothiophene derivative: reversibility and impact on the thin film morphology.

The identification of polymorphs in organic semiconductors allows for establishing structure-property relationships and gaining understanding of microscopic charge transport physics. Thin films of 2,7-bis(octyloxy)[1]benzothieno[3,2-b]-benzothiophene (C8O-BTBT-OC8) exhibit a substrate-induced phase (SIP) that differs from the bulk structure, with important implications for the electrical performance in organic field effect transistors (OFETs). Here we combine grazing incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM) to study how temperature affects the morphology and structure of C8O-BTBT-OC8 films grown by physical vapor deposition on SiO2. We report a structural transition for C8O-BTBT-OC8 films, from the SIP encountered at room temperature (RT) to a high temperature phase (HTP) when the films are annealed at a temperature T ≥ 90 °C. In this HTP structure, the molecules are packed with a tilt angle (≈39° respect to the surface normal) and an enlarged in-plane unit cell. Although the structural transition is reversible on cooling at RT, AFM reveals that molecular layers at the SiO2 interface can remain with the HTP structure, buried under the film ordered in the SIP. For annealing temperatures close to 150 °C, dewetting occurs leading to a more complex morphological and structural scenario upon cooling, with coexistence of different molecular tilts. Because the molecular packing at the interface has direct impact in the charge carrier mobility of OFETs, identifying the different polymorphs of a material in the thin film form and determining their stability at the interfaces are key factors for device optimization.

Tuning Spin Current Injection at Ferromagnet-Nonmagnet Interfaces by Molecular Design.

There is a growing interest in utilizing the distinctive material properties of organic semiconductors for spintronic applications. Here, we explore the injection of pure spin current from Permalloy into a small molecule system based on dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) at ferromagnetic resonance. The unique tunability of organic materials by molecular design allows us to study the impact of interfacial properties on the spin injection efficiency systematically. We show that both the spin injection efficiency at the interface and the spin diffusion length can be tuned sensitively by the interfacial molecular structure and side chain substitution of the molecule.

Deracemization in a Complex Quaternary System with a Second-Order Asymmetric Transformation by Using Phase Diagram Studies.

A productive deracemization process based on a quaternary phase diagram study of a naphthamide derivative is reported. New racemic compounds of an atropisomeric naphthamide derivative have been discovered, and a quaternary phase diagram has been constructed that indicated that four solids are stable in a methanol/H2 O solution. Based on the results of a heterogeneous equilibria study showing the stable domain of the conglomerate, a second-order asymmetric transformation was achieved with up to 97 % ee. Furthermore, this methodology showcases the chiral separation of a stable racemic compound forming system and does not suffer from any of the typical limitations of deracemization, although application is still limited to conglomerate-forming systems. We anticipate that this present study will serve as a fundamental model for the design of sophisticated chiral separation processes.

Deracemization in a Complex Quaternary System with a Second-Order Asymmetric Transformation by Using Phase Diagram Studies.

Invited for the cover of this issue is the group of Gérard Coquerel at Université de Rouen Normandie. The image depicts a pyramid-like tetrahedron of the quaternary phase diagram showing where symmetry breaking can take place. Read the full text of the article at 10.1002/chem.201903338.

N-Doped TiO2 Photocatalyst Coatings Synthesized by a Cold Atmospheric Plasma.

This work presents a simple, fast (20 min treatment), inexpensive, and highly efficient method for synthesizing nitrogen-doped titanium dioxide (N-TiO2) as an enhanced visible light photocatalyst. In this study, N-TiO2 coatings were fabricated by atmospheric pressure dielectric barrier discharge (DBD) at room temperature. The composition and the chemical bonds of the TiO2 and N-TiO2 coatings were characterized by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). The results indicate that the nitrogen element has doped the TiO2 lattice, which was further confirmed by Raman spectroscopy and grazing incidence X-ray diffraction (GIXRD). The doping mechanism was investigated using OES to study the plasma properties under different conditions. It suggests that the NH radicals play a key role in doping TiO2. The concentration of nitrogen in the N-TiO2 coatings can be controlled by changing the concentration of NH3 in the plasma or the applied power to adjust the concentration of NH radicals in the plasma. The band gap of N-TiO2 was reduced after NH3/Ar plasma treatment from 3.25 to 3.18 eV. Consequently, the N-TiO2 coating showed enhanced photocatalytic activity under white-light-emitting-diode (LED) irradiation. The photocatalytic degradation rate for the N-TiO2 coating was about 1.4 times higher than that of the undoped TiO2 coating.

Substrate-Induced Phase of a Benzothiophene Derivative Detected by Mid-Infrared and Lattice Phonon Raman Spectroscopy.

The presence of a substrate-induced polymorph of 2,7-dioctyloxy[1]benzothieno[3,2-b]benzothiophene is probed in microscopic crystals and in thin films. Two experimental techniques are used: lattice phonon Raman and IR spectroscopy. The bulk crystal and substrate-induced phase have an entirely different molecular packing, and therefore, their Raman spectra are characteristic fingerprints of the respective polymorphs. These spectra can be unambiguously assigned to the individual polymorphs. Drop-cast and spin-coated thin films on solid substrates are investigated in the as-prepared state and after solvent-vapor annealing. Because Raman spectroscopy is less sensitive with decreasing film thickness, IR spectroscopy is shown to be a more feasible tool for phase detection. The surface-induced phase is mainly present in the as-prepared thin films, whereas the bulk phase is present after solvent-vapor annealing. This result suggests that the surface-induced phase is a metastable polymorph.

Structural Evolution of an Organic Semiconducting Molecule onto a Soft Substrate.

The structural organization and evolution of the organic semiconducting molecule 2,7-dioctyloxy[1]benzothieno[3,2-b]-benzothiophene on a soft matrix is studied. Thin films of a blend formed from polystyrene and the molecule were prepared by spin-coating onto silicon substrates, which were subsequently studied by using a combination of microscopy and scattering techniques. The organic semiconducting molecule segregated to the surface and developed a phase with a different structure to the bulk, as in the case of a substrate induced phase observed previously. Under a solvent vapor annealing procedure, the growth of micrometer-sized tetragonal crystals onto the polymer surface was observed, which was not evidenced for the silicon substrates.

Semi-metallic polymers.

Polymers are lightweight, flexible, solution-processable materials that are promising for low-cost printed electronics as well as for mass-produced and large-area applications. Previous studies demonstrated that they can possess insulating, semiconducting or metallic properties; here we report that polymers can also be semi-metallic. Semi-metals, exemplified by bismuth, graphite and telluride alloys, have no energy bandgap and a very low density of states at the Fermi level. Furthermore, they typically have a higher Seebeck coefficient and lower thermal conductivities compared with metals, thus being suitable for thermoelectric applications. We measure the thermoelectric properties of various poly(3,4-ethylenedioxythiophene) samples, and observe a marked increase in the Seebeck coefficient when the electrical conductivity is enhanced through molecular organization. This initiates the transition from a Fermi glass to a semi-metal. The high Seebeck value, the metallic conductivity at room temperature and the absence of unpaired electron spins makes polymer semi-metals attractive for thermoelectrics and spintronics.

Investigation of the Qx -Qy Equilibrium in a Metal-Free Phthalocyanine.

Phthalocyanines (Pcs) have attracted a lot of interest as small molecules for organic electronics. However, some excited-state properties of metal-free phthalocyanines, as for example, the dynamics of the transition between the nondegenerate Qx and Qy states in a metal-free phthalocyanine, have not been fully established. This effect results in a blue-shifted shoulder with low intensity in the Pc fluorescence spectrum. This shoulder was suggested to be related to emission from the more energetic Qy state. By using ultrafast femtosecond transient absorption, we have found a clear equilibrium between the Qx and Qy state of metal-free phthalocyanines in solution.

Polymorphism of dioctyl-terthiophene within thin films: The role of the first monolayer.

The origins of specific polymorphic phases within thin films are still not well understood. The polymorphism of the molecule dioctyl-terthiophene is investigated during the presence of a silicon-oxide surface during the crystallisation process. It is found that a monolayer of molecules forms two-dimensional crystals on the surface. In the case of thicker films crystalline islands are formed, a comparison of the three polymorphic phases observed within thin films and the thermodynamically more stable single crystal phases reveals distinct differences which can be related to an adaption of the molecular packing with the flat surface of the substrate.

Coherence in Polycrystalline Thin Films of Twisted Molecular Crystals.

Helicoidal crystallites in rhythmically banded spherulites manifest spectacular optical patterns in small molecules and polymers. It is shown that concentric optical bands indicating crystallographic orientations typically lose coherence (in-phase twisting) with growth from the center of nucleation. Here, coherence is shown to increase as the twist period decreases for seven molecular crystals grown from the melt. This dependence was correlated to crystallite fiber thickness and length, as well as crystallite branching frequency, a parameter that was extracted from scanning electron micrographs, and supported by numerical simulations. Hole mobilities for 2,5-didodecyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP-C12) measured by using organic field-effect transistors demonstrated that more incoherent boundaries between optical bands in spherulites lead to higher charge transport for films with the same twist period. This was rationalized by combining our growth model with electrodynamic simulations. This work illustrates the emergence of complexity in crystallization processes (spherulite formation) that arises in the extra variable of helicoidal radial twisting. The details of the patterns analyzed here link the added complexity in crystal growth to the electronic and optical properties of the thin films.

Dynamics of monolayer-island transitions in 2,7-dioctyl-benzothienobenzthiophene thin films.

The order in molecular monolayers is a crucial aspect for their technological application. However, the preparation of defined monolayers by spin-coating is a challenge, since the involved processes are far from thermodynamic equilibrium. In the work reported herein, the dynamic formation of dioctyl-benzothienobenzothiophene monolayers is explored as a function of temperature by using X-ray scattering techniques and atomic force microscopy. Starting with a disordered monolayer after the spin-coating process, post-deposition self-reassembly at room temperature transforms the initially amorphous layer into a well-ordered bilayer structure with a molecular herringbone packing, whereas at elevated temperature the formation of crystalline islands occurs. At the temperature of the liquid-crystalline crystal-smectic transition, rewetting of the surface follows resulting in a complete homogeneous monolayer. By subsequent controlled cooling to room temperature, cooling-rate-dependent kinetics is observed; at rapid cooling, a stable monolayer is preserved at room temperature, whereas slow cooling causes bilayer structures. Increasing the understanding and control of monolayer formation is of high relevance for achieving ordered functional monolayers with defined two-dimensional packing, for future applications in the field of organic electronics.

Synthesis of 1,6-, 2,7-, 3,8-, and 4,9-isomers of didodecyl[1]benzothieno[3,2-b][1]benzothiophenes.

The synthesis of 1,6-, 2,7-, 3,8-, and 4,9-isomers of dibromo- and didodecyl[1]benzothieno[3,2-b][1]benzothiophenes, via the stilbene pathway, is described. Starting from the synthesis of bromo-2-(methylthio)benzaldehydes, a series of functionalization, McMurry coupling, and finalising cyclization reactions were explored. The stereochemistry of the cyclization mechanism was investigated. Using this methodology didodecyl[1]benzothieno[3,2-b][1]benzothiophenes were formed in overall yields of 5-32%.

Doping of organic semiconductors: impact of dopant strength and electronic coupling.

Molecular doping: The standard model for molecular p-doping of organic semiconductors (OSCs) assumes integer charge transfer between OSC and dopant. This is in contrast to an alternative model based on intermolecular complex formation instead. By systematically varying the acceptor strength it was possible to discriminate the two models. The latter is clearly favored, suggesting strategies for the chemical design of more efficient molecular dopants.

Interlayer Sliding Phonon Drives Phase Transition in the Ph-BTBT-10 Organic Semiconductor.

In the field of organic electronics, the semiconductor 7-decyl-2-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10) has become a benchmark due to its high charge mobility and chemical stability in thin film devices. Its phase diagram is characterized by a crystal phase with a bilayer structure that at high temperature transforms into a Smectic E liquid crystal with monolayer structure. As the charge transport properties appear to depend on the phase present in the thin film, the transition has been the subject of structural and computational studies. Here such a process has been investigated by polarized low frequency Raman spectroscopy, selectively probing the intermolecular dynamics of the two phases. The spectroscopic observations demonstrate the key role played by a displacive component of the transition, with the interpenetration of the crystal bilayers driven by lattice phonon mode softening followed by the intralayer rearrangement of the molecule rigid cores into the herringbone motif of the liquid crystal. The mechanism can be related to the effectiveness of thermal annealing to restore the crystal phase in films.

Mechanistic View on the Order-Disorder Phase Transition in Amphidynamic Crystals.

We combine temperature-dependent low-frequency Raman measurements and first-principles calculations to obtain a mechanistic understanding of the order-disorder phase transition of 2,7-di-tert-butylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene (ditBu-BTBT) and 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) semiconducting amphidynamic crystals. We identify the lattice normal modes associated with the phase transition by following the position and width of the Raman peaks with temperature and identifying peaks that exhibit nonlinear dependence toward the phase transition temperature. Our findings are interpreted according to the "hardcore mode" model previously used to describe order-disorder phase transitions in inorganic and hybrid crystals with a Brownian sublattice. Within the framework of this model, ditBu-BTBT exhibits an ideal behavior where only one lattice mode is associated with the phase transition. TIPS-pentacene deviates strongly from the model due to strong interactions between lattice modes. We discuss the origin of the different behaviors and suggest side-chain engineering as a tool to control polymorphism in amphidynamic crystals.