Programmed self-assembly of large π-conjugated molecules into electroactive one-dimensional nanostructures

Abstract

Electroactive one-dimensional (1D) nano-objects possess inherent unidirectional charge and energy transport capabilities along with anisotropic absorption and emission of light, which are of great advantage for the development of nanometer-scale electronics and optoelectronics. In particular, molecular nanowires formed by self-assembly of π-conjugated molecules attract increasing attention for application in supramolecular electronics. This review introduces recent topics related to electroactive molecular nanowires. The nanowires are classified into four categories with respect to the electronic states of the constituent molecules: electron donors, acceptors, donor–acceptor pairs and miscellaneous molecules that display interesting electronic properties. Although many challenges still remain for practical use, state-of-the-art 1D supramolecular nanomaterials have already brought significant advances to both fundamental chemical sciences and technological applications.     

Tuning the Optical and Electrical Properties of Few‐Layer Black Phosphorus via Physisorption of Small Solvent Molecules

Black phosphorus (BP) is recently becoming more and more popular among semiconducting 2D materials for (opto)electronic applications. The controlled physisorption of molecules on the BP surface is a viable approach to modulate its optical and electronic properties. Solvents consisting of small molecules are often used for washing 2D materials or as liquid media for their chemical functionalization with larger molecules, disregarding their ability to change the opto‐electronic properties of BP. Herein, it is shown that the opto‐electronic properties of mechanically exfoliated few‐layer BP are altered when physically interacting with common solvents. Significantly, charge transport analysis in field‐effect transistors reveals that physisorbed solvent molecules induce a modulation of the charge carrier density which can be as high as 10¹² cm^?2 in BP, i.e., comparable to common dopants such as F₄‐TCNQ and MoO₃. By combining experimental evidences with density functional theory calculations, it is confirmed that BP doping by solvent molecules not only depends on charge transfer, but is also influenced by molecular dipole. The results clearly demonstrate how an exquisite tuning of the opto‐electronic properties of few‐layer BP can be achieved through physisorption of small solvent molecules. Such findings are of interest both for fundamental studies and more technological applications in opto‐electronics.     

Guided Molecular Assembly on a Locally Reactive 2D Material

Atomically precise engineering of the position of molecular adsorbates on surfaces of 2D materials is key to their development in applications ranging from catalysis to single‐molecule spintronics. Here, stable room‐temperature templating of individual molecules with localized electronic states on the surface of a locally reactive 2D material, silicene grown on ZrB₂, is demonstrated. Using a combination of scanning tunneling microscopy and density functional theory, it is shown that the binding of iron phthalocyanine (FePc) molecules is mediated via the strong chemisorption of the central Fe atom to the sp³‐like dangling bond of Si atoms in the linear silicene domain boundaries. Since the planar Pc ligand couples to the Fe atom mostly through the in‐plane d orbitals, localized electronic states resembling those of the free molecule can be resolved. Furthermore, rotation of the molecule is restrained because of charge rearrangement induced by the bonding. These results highlight how nanoscale changes can induce reactivity in 2D materials, which can provide unique surface interactions for enabling novel forms of guided molecular assembly.     

Thermoresponsive Emission Switching via Lower Critical Solution Temperature Behavior of Organic–Inorganic Perovskite Nanoparticles

Lead halide perovskites have shown much promise for high‐performing solar cells due to their inherent electronic nature, and though the color of bright‐light emitters based on perovskite nanoparticles can be tuned by halide mixing and/or size control, dynamic switching using external stimuli remains a challenge. This article reports an unprecedented lower critical solution temperature (LCST) for toluene solutions containing methylammonium lead bromide (MAPbBr₃), oleic acid, alkylamines, and dimethylformamide. The delicate interplay of these molecules and ions allows for the reversible formation and decomposition of MAPbBr₃ nanoparticles upon heating and cooling, which is accompanied by green and blue photoemissions at each state. An intermediate 1D crystal with PbBr₂‐amine coordination is found to play pivotal role in this, and a mechanistic insight is provided based on a three‐state model. In addition to a high quantum yield (up to 85%), this system allows for control over the cloud point (30?80 °C) through compositional engineering and the luminescent color (blue to red) via halogen exchange, thus making it a versatile solution for developing functional molecular organic–inorganic LCST quantum dots.     

Rigid dimers formed through strong interdigitated H-bonds yield compact 1D supramolecular helical polymers

Hierarchical self-assembly of small abiotic molecular modules interacting through noncovalent forces is increasingly being used to generate functional structures and materials for electronic, catalytic, and biomedical applications. The greatest control over the geometry in H-bond supramolecular architectures, especially in H-bonded supramolecular polymers, can be achieved by using conformationally rigid molecular modules undergoing self-assembly through strong H-bonds. Their binding strength depends on the multiplicity of the H-bonds, the nature of donor/acceptor pairs and their secondary attractive/repulsive interactions. Here a functionalized molecular module is described, which is capable of self-associating through self-complementary H-bonding patterns comprising four strong and two medium-strength H-bonds to form dimers. The self-association of these phenylpyrimidine-based dimers through directional H-bonding between two lateral pyridin-2(1H)-one units of neighboring molecules allows the formation of highly compact 1D supramolecular polymers by self-assembly on graphite. A concentration-dependent study by scanning tunneling microscopy at the solid-liquid interface, corroborated by dispersion-corrected density functional studies, reveals the controlled generation of either linear supramolecular 2D arrays, or long helical supramolecular polymers with a high shape persistence.     

Molecular Approach to Electrochemically Switchable Monolayer MoS2 Transistors

As Moore's law is running to its physical limit, tomorrow's electronic systems can be leveraged to a higher value by integrating “More than Moore” technologies into CMOS digital circuits. The hybrid heterostructure composed of two-dimensional (2D) semiconductors and molecular materials represents a powerful strategy to confer new properties to the former components, realize stimuli-responsive functional devices, and enable diversification in “More than Moore” technologies. Here, an ionic liquid (IL) gated 2D MoS₂ field-effect transistor (FET) with molecular functionalization is fabricated. The suitably designed ferrocene-substituted alkanethiol molecules not only improve the FET performance, but also show reversible electrochemical switching on the surface of MoS₂. Field-effect mobility of monolayer MoS₂ reaches values as high as ≈116 cm² V⁻¹ s⁻¹ with I_on/I_off ratio exceeding 10⁵. Molecules in their neutral or charged state impose distinct doping effect, efficiently tuning the electron density in monolayer MoS₂. It is noteworthy that the joint doping effect from IL and switchable molecules results in the steep subthreshold swing of MoS₂ FET in the backward sweep. These results demonstrate that the device architecture represents an unprecedented and powerful strategy to fabricate switchable 2D FET with a chemically programmed electrochemical signal as a remote control, paving the road toward novel functional devices.     

Water-soluble organo-silica hybrid nanowires

There has been growing interest in the past decade in one-dimensional (1D) nanostructures, such as nanowires, nanotubes or nanorods, owing to their size-dependent optical and electronic properties and their potential application as building blocks, interconnects and functional components for assembling nanodevices. Significant progress has been made; however, the strict control of the distinctive geometry at extremely small size for 1D structures remains a great challenge in this field. The anisotropic nature of cylindrical polymer brushes has been applied to template 1D nanostructured materials, such as metal, semiconductor or magnetic nanowires. Here, by constructing the cylindrical polymer brushes themselves with a precursor-containing monomer, we successfully synthesized hybrid nanowires with a silsesquioxane core and a shell made up from oligo(ethylene glycol) methacrylate units, which are soluble in water and many organic solvents. The length and diameter of these rigid wires are tunable by the degrees of polymerization of both the backbone and the side chain. They show lyotropic liquid-crystalline behaviour and can be pyrolysed to silica nanowires. This approach provides a route to the controlled fabrication of inorganic or hybrid silica nanostructures by living polymerization techniques.     

Controlling Electronic States and Transport Properties at the Level of Single Molecules

Since molecular electronics has been rapidly growing as a promising alternative to conventional electronics towards the ultimate miniaturization of electronic devices through the bottom‐up strategy, it has become a long‐term desire to understand and control the transport properties at the level of single molecules. In this Research News article it is shown that one may modify the electronic states of single molecules and thus control their transport properties through designing and fabrication of functional molecules or manipulating molecules with scanning tunneling microscopy. The rectifying effect of single molecules can be realized by designing a donor–barrier–acceptor architecture of Pyridine–σ–C₆₀ molecules to achieve the Aviram–Ratner rectifier and by modifying electronic states through azafullerene C₅₉N molecules. The effect of the negative differential resistances can be realized by appropriately matching the molecular orbital symmetries between a cobalt phthalocyanine (CoPc) molecule and a Ni electrode. The electronic states and transport properties of single molecules, such as CoPc and melamine molecules, can be altered through manipulation or modifying molecular structures, leading to functionalized molecular devices.     

A molecular scale full adder based on controlled intramolecular electron and energy transfer

Electron and electronic energy transfer processes are ways by which different molecules can signal their state from one (the Donor, D) to the other (the Acceptor, A). This transfer is often studied as an intermolecular process but it can also occur intramolecularly, that is between two bridged parts of a bichromophoric molecule.We show that the donor part of a bichromophore molecule can communicate its logic output as input to the acceptor part of the bichromophoric molecule. Such transfer is achieved through electronic energy transfer between the chromophores. We discuss a specific pair, the rhodamine 6G-azulene, for which there is considerable data, but the scheme is general enough to allow a wide choice of D–A pairs. We present preliminary results pertaining to a newly synthesized bichromophoric molecule based on this pair, in which a full adder is implemented, utilizing intramolecular electronic energy transfer between the two moieties.     

Application Challenges in Fiber and Textile Electronics

Modern electronic devices are moving toward miniaturization and integration with an emerging focus on wearable electronics. Due to their close contact with the human body, wearable electronics have new requirements including low weight, small size, and flexibility. Conventional 3D and 2D electronic devices fail to efficiently meet these requirements due to their rigidity and bulkiness. Hence, a new family of 1D fiber-shaped electronic devices including energy-harvesting devices, energy-storage devices, light-emitting devices, and sensing devices has risen to the challenge due to their small diameter, lightweight, flexibility, and weavability into soft textile electronics. The application challenges faced by fiber and textile electronics from single fiber-shaped devices to continuously scalable fabrication, to encapsulation and testing, and to application mode exploration, are discussed. The evolutionary trends of fiber and textile electronics are then summarized. Finally, future directions required to boost their commercialization are highlighted.     

Metallic conduction at organic charge-transfer interfaces

The electronic properties of interfaces between two different solids can differ strikingly from those of the constituent materials. For instance, metallic conductivity-and even superconductivity-have recently been discovered at interfaces formed by insulating transition-metal oxides. Here, we investigate interfaces between crystals of conjugated organic molecules, which are large-gap undoped semiconductors, that is, essentially insulators. We find that highly conducting interfaces can be realized with resistivity ranging from 1 to 30 kohms per square, and that, for the best samples, the temperature dependence of the conductivity is metallic. The observed electrical conduction originates from a large transfer of charge between the two crystals that takes place at the interface, on a molecular scale. As the interface assembly process is simple and can be applied to crystals of virtually any conjugated molecule, the conducting interfaces described here represent the first examples of a new class of electronic systems.     

Synthesis,structure and photocatalysis properties of two 3D Isostructural Ln (Ⅲ)-MOFs based 2,6-Pyridinedicarboxylic acid

Two new 3 D metal-organic frameworks(MOFs) named [Pr_2(PDA)3-3 H_2 O]-H_2 O(1) and[Nd_2(PDA)3-3 H_2 O] H_2 O(_2) [2,6-Pyridinedicarboxylic acid(H2 PDA)] were synthesized by solvothermal method. They were characterized by elemental analyses(EA), infrared spectroscopy(FT-IR), thermogravimetric analysis(TG), photocatalysis performance and single crystal X-ray diffraction studies(XRD).The XRD analysis indicated that MOFs(1) and(2) both belong to the monoclinic system with space group P2(1)/C. The structural model were drawn by the diamond software, and the structure revel that MOFs(1) and(2) adopt three-dimensional(3 D) frameworks constructed by cross-linking of one-dimensional(1 D) infinite chain secondary building unit(SBU) by 2,6-Pyridinedicarboxylic acid and hydrogen bond as linker. These frameworks feature channels inside which coordinated H_20 solvent molecules are located. Thermogravimetric analysis showed that both MOFs are thermally stable, the photocatalytic evaluation showed the materials have a good prospect in degration methylene blue. As for complex1, the decomposition efficiency of Methylene blue was about 91.08% after 130 min and the complex 2 reach 90.45% after 160 min under the sun light.     

Control of electron transfer from lead-salt nanocrystals to TiO₂

The roles of solvent reorganization energy and electronic coupling strength on the transfer of photoexcited electrons from PbS nanocrystals to TiO(2) nanoparticles are investigated. We find that the electron transfer depends only weakly on the solvent, in contrast to the strong dependence in the nanocrystal-molecule system. This is ascribed to the larger size of the acceptor in this system, and is accounted for by Marcus theory. The electronic coupling of the PbS and TiO(2) is varied by changing the length, aliphatic and aromatic structure, and anchor groups of the linker molecules. Shorter linker molecules consistently lead to faster electron transfer. Surprisingly, linker molecules of the same length but distinct chemical structures yield similar electron transfer rates. In contrast, the electron transfer rate can vary dramatically with different anchor groups.     

食品添加剂二氧化碳中苯系列气体标准物质的研究

研究了注射重量法制备食品添加剂二氧化碳中苯系列气体标准物质的实验方法。气体称量装置采用日本Kyoto公司H2-30K型低感量大量程机械天平（30kg,1mg）和瑞士Mettler公司SB-16001粗称气瓶的大量程低灵敏度电子天平（16kg,0.1g）,称量组分气体和稀释气体。用日本Shimadzu L-200D高精密天平（200g,0.05mg）称量带锁注射器注射前后的重量。实验中选取苯含量低于0.01×10^-6的高纯二氧化碳气体,以满足配制1×10^-6标准气体的需求,本项研究苯系列气体标准物质重量制备的不确定度均小于2%。     

Large‐Scale Growth and Field‐Effect Transistors Electrical Engineering of Atomic‐Layer SnS2

2D layers of metal dichalcogenides are of considerable interest for high‐performance electronic devices for their unique electronic properties and atomically thin geometry. 2D SnS₂ nanosheets with a bandgap of ≈2.6 eV have been attracting intensive attention as one potential candidate for modern electrocatalysis, electronic, and/or optoelectronic fields. However, the controllable growth of large‐size and high‐quality SnS₂ atomic layers still remains a challenge. Herein, a salt‐assisted chemical vapor deposition method is provided to synthesize atomic‐layer SnS₂ with a large crystal size up to 410 µm and good uniformity. Particularly, the as‐fabricated SnS₂ nanosheet‐based field‐effect transistors (FETs) show high mobility (2.58 cm² V^?1 s^?1) and high on/off ratio (≈10⁸), which is superior to other reported SnS₂‐based FETs. Additionally, the effects of temperature on the electrical properties are systematically investigated. It is shown that the scattering mechanism transforms from charged impurities scattering to electron–phonon scattering with the temperature. Moreover, SnS₂ can serve as an ideal material for energy storage and catalyst support. The high performance together with controllable growth of SnS₂ endow it with great potential for future applications in electrocatalysis, electronics, and optoelectronics.     

Magnetic properties of ZnO nanoparticles

We experimentally show that it is possible to induce room-temperature ferromagnetic-like behavior in ZnO nanoparticles without doping with magnetic impurities but simply inducing an alteration of their electronic configuration. Capping ZnO nanoparticles ( approximately 10 nm size) with different organic molecules produces an alteration of their electronic configuration that depends on the particular molecule, as evidenced by photoluminescence and X-ray absorption spectroscopies and altering their magnetic properties that varies from diamagnetic to ferromagnetic-like behavior.     

Preparation and properties of active submicronic solids and new metastable phases obtained via a metal-organic precursor method

The mixing of constituent ions on an atomic scale accomplished in single phase metal-organic precursors facilitates the occurrence and completion of the reactions such as decomposition, oxidation and reduction at reduced temperatures and in shorter times. This has been particularly shown for the first series of transition metals and for the lanthanide elements for which simple, and mixed oxides or their oxide solid-solutions have been prepared via decomposition and treatment of their respective organic salt precursors. The method gives compounds with increased homogeneity, purity and reactivity and allows isolation of submicronic solids and sometimes of new metastable phases, which could not have been obtained by high-temperature reactions. The morphological and other application properties of these submicronic solids and of new metastable phases can be widely modified and regulated by varying the composition and treatment given to the metal-organic precursors.     

Gas-induced transformation and expansion of a non-porous organic solid

Organic solids composed by weak van der Waals forces are attracting considerable attention owing to their potential applications in gas storage, separation and sensor applications. Herein we report a gas-induced transformation that remarkably converts the high-density guest-free form of a well-known organic host (p-tert-butylcalix[4]arene) to a low-density form and vice versa, a process that would be expected to involve surmounting a considerable energy barrier. This transformation occurs despite the fact that the high-density form is devoid of channels or pores. Gas molecules seem to diffuse through the non-porous solid into small lattice voids, and initiate the transition to the low-density kinetic form with approximately 10% expansion of the crystalline organic lattice, which corresponds to absorption of CO2 and N2O (refs 4,5). This suggests the possibility of a more general phenomenon that can be exploited to find more porous materials from non-porous organic and metal-organic frameworks that possess void space large enough to accommodate the gas molecules.     

Controllable Bipolar Doping of Graphene with 2D Molecular Dopants

The fine control of graphene doping levels over a wide energy range remains a challenging issue for the electronic applications of graphene. Here, the controllable doping of chemical vapor deposited graphene, which provides a wide range of energy levels (shifts up to ± 0.5 eV), is demonstrated through physical contact with chemically versatile graphene oxide (GO) sheets, a 2D dopant that can be solution‐processed. GO sheets are a p‐type dopant due to their abundance of electron‐withdrawing functional groups. To expand the energy window of GO‐doped graphene, the GO surface is chemically modified with electron‐donating ethylene diamine molecules. The amine‐functionalized GO sheets exhibit strong n‐type doping behaviors. In addition, the particular physicochemical characteristics of the GO sheets, namely their sheet sizes, number of layers, and degree of oxidation and amine functionality, are systematically varied to finely tune their energy levels. Finally, the tailor‐made GO sheet dopants are applied into graphene‐based electronic devices, which are found to exhibit improved device performances. These results demonstrate the potential of GO sheet dopants in many graphene‐based electronics applications.     

Wide-gap layered oxychalcogenide semiconductors: Materials, electronic structures and optoelectronic properties

Applying the concept of materials design for transparent conductive oxides to layered oxychalcogenides, several p-type and n-type layered oxychalcogenides were proposed as wide-gap semiconductors and their basic optical and electrical properties were examined. The layered oxychalcogenides are composed of ionic oxide layers and covalent chalcogenide layers, which bring wide-gap and conductive properties to these materials, respectively. The electronic structures of the materials were examined by normal/inverse photoemission spectroscopy and energy band calculations. The results of the examinations suggested that these materials possess unique features more than simple wide-gap semiconductors. Namely, the layered oxychalcogenides are considered to be extremely thin quantum wells composed of the oxide and chalcogenide layers or 2D chalcogenide crystals/molecules embedded in an oxide matrix. Observation of step-like absorption edges, large band gap energy and large exciton binding energy demonstrated these features originating from 2D density of states and quantum size effects in these layered materials.