Zeyi Tu

A two-dimensional π–d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour

Currently, studies on organic two-dimensional (2D) materials with special optic-electronic properties are attracting great research interest. However, 2D organic systems possessing promising electrical transport properties are still rare. Here a highly crystalline thin film of a copper coordination polymer, Cu-BHT (BHT=benzenehexathiol), is prepared via a liquid–liquid interface reaction between BHT/dichloromethane and copper(II) nitrate/H2O. The morphology and structure characterization reveal that this film is piled up by nanosheets of 2D lattice of [Cu3(C6S6)]n, which is further verified by quantum simulation. Four-probe measurements show that the room temperature conductivity of this material can reach up to 1,580 S cm−1, which is the highest value ever reported for coordination polymers. Meanwhile, it displays ambipolar charge transport behaviour and extremely high electron and hole mobilities (99 cm2 V−1 s−1 for holes and 116 cm2 V−1 s−1 for electrons) under field-effect modulation.

Tuning the Crystal Polymorphs of Alkyl Thienoacene via Solution Self‐Assembly Toward Air‐Stable and High‐Performance Organic Field‐Effect Transistors

The first example for thienoacene derivatives with selective growth of different crystal polymorphs is simply achieved by solution-phase self-assembly. Compared with platelet-shaped α-phase crystals, organic field-effect transistors (OFETs) based on microribbon-shaped β-phase crystals show a hole mobility up to 18.9 cm(2) V(-1) s(-1), which is one of the highest values for p-type organic semiconductors measured under ambient conditions.

Hydrogen substituted graphdiyne as carbon-rich flexible electrode for lithium and sodium ion batteries

Organic electrodes are potential alternatives to current inorganic electrode materials for lithium ion and sodium ion batteries powering portable and wearable electronics, in terms of their mechanical flexibility, function tunability and low cost. However, the low capacity, poor rate performance and rapid capacity degradation impede their practical application. Here, we concentrate on the molecular design for improved conductivity and capacity, and favorable bulk ion transport. Through an in situ cross-coupling reaction of triethynylbenzene on copper foil, the carbon-rich frame hydrogen substituted graphdiyne film is fabricated. The organic film can act as free-standing flexible electrode for both lithium ion and sodium ion batteries, and large reversible capacities of 1050 mAh g−1 for lithium ion batteries and 650 mAh g−1 for sodium ion batteries are achieved. The electrode also shows a superior rate and cycle performances owing to the extended π-conjugated system, and the hierarchical pore bulk with large surface area.Flexible batteries have been used to power wearable smart electronics and implantable medical devices. Here, the authors report a carbon-rich flexible hydrogen substituted graphdiyne electrode exhibiting superior electrochemical performance in lithium and sodium ion batteries.

Nitrogen-Doped Porous Graphdiyne: A Highly Efficient Metal-Free Electrocatalyst for Oxygen Reduction Reaction

Metal-free catalysts for oxygen reduction reaction (ORR) are the desired materials for low-cost proton exchange membrane fuel cells. Graphdiyne (GDY), a novel type of two-dimensional carbon allotrope, is featured by its sp- and sp2-hybridized carbon atoms, different from the other existing carbon materials. Thus, nitrogen (N) can be doped in new styles by substituting sp-hybridized carbon atoms, effective for ORR, which has been displayed in this study using both experimental and theoretical technologies. The N-doped GDY was synthesized with pyridine and NH3 as N sources successively, expressing an electrocatalytic activity at a potential above 0.8 V similar to that of commercial Pt/C for ORR in alkaline solution and higher stability and better methanol tolerance than those of Pt/C.

Synthesis of Chlorine-Substituted Graphdiyne and Applications for Lithium-Ion Storage

Chlorine-substituted graphdiyne (Cl-GDY) is prepared through a Glaser-Hay coupling reaction on the copper foil. Cl-GDY is endowed with a unique π-conjugated carbon skeleton with expanded pore size in two dimensions, having graphdiyne-like sp- and sp2 - hybridized carbon atoms. As a result, the transfer tunnels for lithium (Li) ions in the perpendicular direction of the molecular plane are enlarged. Moreover, benefiting from the bottom-to-up fabrication procedure of graphdiyne and the strong chemical tailorability of the alkinyl-contained monomer, the amount of substitutional chlorine atoms with appropriate electronegativity and atom size is high and evenly distributed on the as-prepared carbon framework, which will synergistically stabilize the Li intercalated in the Cl-GDY framework, and thus generate more Li storage sites. Profiting from the above unique structure, Cl-GDY shows remarkable electrochemical properties in lithium ion half-cells.

Ambipolar charge-transport properties in 4,10-dihalogenated anthanthrone crystals: a theoretical study

The charge-transport parameters in three 4,10-dihalogenated anthanthrones (AAOs) are investigated by means of density functional theory (DFT) and molecular dynamics (MD) calculations. Our calculations point to similar hole and electron reorganization energies for each molecule. Significant electronic couplings and bandwidths (particularly for electron transport) are found along the parallel π–π stacking directions in all the dihalogenated AAO crystals. The calculated effective masses are small or moderate for both holes and electrons. Especially for the iodinated AAO crystals, remarkable ambipolar charge transport can be anticipated due to the smallest and similar effective masses for holes and electrons (both are around 1.0 m0). In addition, due to the presence of two small effective masses, two-dimensional charge transport would take place for electrons in the chlorinated AAO crystal and for both holes and electrons in the iodinated AAO crystal. Also, our calculations reveal large nonlocal electron–phonon couplings along the π-stacks in the brominated AAO and, in particular, the chlorinated AAO crystals, which can further improve the balance in transport of holes and electrons.

Shape-Controlled Metal-Free Catalysts: Facet-Sensitive Catalytic Activity Induced by the Arrangement Pattern of Noncovalent Supramolecular Chains

Metal-free catalytic materials have recently received broad attention as promising alternatives to metal-involved catalysts. This is owing to their inherent capability to overcome the inevitable limitations of metal-involved catalysts, such as high sensitivity to poisoning, the limited reserves, high cost and scarcity of metals (especially noble metals), etc. However, the lack of shape-controlled metal-free catalysts with well-defined facets is a formidable bottleneck limiting our understandings on the underlying structure-activity relationship at atomic/molecular level, which thereby restrains their rational design. Here, we report that catalytically active crystals of a porphyrin, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, could be shaped into well-defined cubes and sheet-like tetradecahedrons (TDHD), which are exclusively and predominantly enclosed by {101} and {001} facets, respectively. Fascinatingly, compared to the cubes, the TDHDs display substantially enhanced catalytic activity toward water decontamination under visible-light irradiation, although both the architectures have identical crystalline structure. We disclose that such interesting shape-sensitive catalytic activity is ascribed to the distinct spatial separation efficiency of photogenerated electrons and holes induced by single-channel and multichannel charge transport pathways along noncovalent supramolecular chains, which are arranged as parallel-aligned and 2D network patterns, respectively. Our findings provide an ideal scientific platform to guide the rational design of next-generation metal-free catalysts of desired catalytic performances.

The position effect of an ethynyl spacer on the carrier mobility of anthracene derivatives

Two oxidation-stable naphthalenyl ethynyl anthracene derivatives have been synthesized via Sonogashira coupling. In contrast to a 1-position substituted anthracene derivative with near zero mobility, the functionalization at the 2-position of anthracene gives rise to a densely packed structure and a uniform film with mobility up to 1.6 cm2 V−1 s−1, which is one of the highest values for thin film transistors based on anthracene derivatives.

A novel angularly fused bistetracene: facile synthesis, crystal packing and single-crystal field effect transistors

We report a facile synthesis of novel angularly fused bistetracene derivatives where two tetracene skeletons are cata-annulated at three benzene rings. Compared with previously described examples, our bistetracenes exhibit a narrower HOMO–LUMO gap but still exhibit high stability. Attempted synthesis of di-substituted bistetracene (BT-2TIPS) also led to unexpected triple (BT-3TIPS) and four-fold (BT-4TIPS) alkylsilylethynyl substitution. The photophysical, electrochemical and optical properties as well as the solid-state structure of these three bistetracene analogues are investigated. A charge carrier mobility up to 0.42 cm2 V−1 s−1 was determined based on field effect transistors.

Bottom-up growth of n-type monolayer molecular crystals on polymeric substrate for optoelectronic device applications

Self-assembly of monolayers of functional molecules on dielectric surfaces is a promising approach for the development of molecular devices proposed in the 1970s. Substrate chemically bonded self-assembled monolayers of semiconducting conjugated molecules exhibit low mobility. And self-assembled monolayer molecular crystals are difficult to scale up and limited to growth on substrates terminated by hydroxyl groups, which makes it difficult to realize sophisticated device functions, particularly for those relying on n-type electron transport, as electrons suffer severe charge trapping on hydroxyl terminated surfaces. Here we report a gravity-assisted, two-dimensional spatial confinement method for bottom-up growth of high-quality n-type single-crystalline monolayers over large, centimeter-sized areas. We demonstrate that by this method, n-type monolayer molecular crystals with high field-effect mobility of 1.24 cm2 V−1 s−1 and band-like transport characteristics can be grown on hydroxyl-free polymer surface. Furthermore, we used these monolayer molecular crystals to realize high-performance crystalline, gate-/light-tunable lateral organic p–n diodes.New methods for obtaining large-area monolayer molecular crystals (MMCs) on hydrophobic surfaces are needed to realize the full potential of MMCs for organic electronics. Here, the authors demonstrate bottom-up growth of high-grade n-type MMCs, which show superior performance in device applications.