含苝单元聚合物的合成及光学性能

利用酐为原料合成出N,N′-二(间羟基苯基)二酰亚胺,再通过与TDI(2,4-甲苯二异氰酸酯)的共聚合成了具有酰亚胺单元的P-π共轭聚合物,利用IR、UV-Vis、元素分析和热重分析对其结构进行了表征。并利用四波混频方法测定了该聚合物的三阶非线性,其响应系数达1.39×10-13esu,响应时间为132.59fs。另外,测得其溶液具有较高的荧光发射强度。     

Solution processible naphthalene and perylene bisimides: Synthesis,electrochemical characterization and application to organic field effect transistors (OFETs) fabrication

A series of alkyl- or alkylphenyl-1,4,5,8-naphthalenetetracarboxylic-1,4:5,8-bisimides together with the comparative series of the corresponding 3,4,9,10-perylenetetracarboxylic-3,4:9,10-bisimides have been synthesized and characterized by cyclic voltammetry. The naphthalene bisimides family shows a clear dependence of its first reduction potential – corresponding to the LUMO level – on the nature of the N-substituent. Naphthalene bisimides containing alkylphenyl groups undergo the first 1e reduction at potentials of ca. 100 mV higher than those with alkyl groups (ca. −900 mV vs ca. −1000 mV with respect to Fc/Fc⁺ couple). No effect of the nature of the substituent is observed for the corresponding perylene bisimide series. Due to their improved solution processibility the synthesized organic semiconductors can be used for the fabrication of all organic, flexible n-channel field effect transistors (OFETs) through spin coating and printing techniques, without the necessity of the use of vacuum deposition techniques. The best of the fabricated transistors, operating in air show the charge carriers mobility of 4 × 10⁻² cm²/(V s) and the ON/OFF ratio equal to 4.5 × 10⁵.     

苝纳米片的制备和光学特性

利用再沉淀法将Perylene/THF溶液注入甲醇和水的混合溶剂中制备了苝纳米薄片,采用扫描电镜（SEM）、吸收光谱对纳米片形貌和光学特性进行了表征,结果表明,注入不同体积Perylene/THF溶液的苝纳米片表现出不同光学特性,同时对纳米片的形成机制进行了初步的分析和探讨。     

Novel Insoluble Organic Cathodes for Advanced Organic K‐Ion Batteries

Organic redox‐active molecules are inborn electrodes to store large‐radius potassium (K) ion. High‐performance organic cathodes are important for practical usage of organic potassium‐ion batteries (OPIBs). However, small‐molecule organic cathodes face serious dissolution problems against liquid electrolytes. A novel insoluble small‐molecule organic cathode [N,N′‐bis(2‐anthraquinone)]‐perylene‐3,4,9,10‐tetracarboxydiimide (PTCDI‐DAQ, 200 mAh g^?1) is initially designed for OPIBs. In half cells (1–3.8 V vs K⁺/K) using 1 m KPF₆ in dimethoxyethane (DME), PTCDI‐DAQ delivers a highly stable specific capacity of 216 mAh g^?1 and still holds the value of 133 mAh g^?1 at an ultrahigh current density of 20 A g^?1 (100 C). Using reduced potassium terephthalate (K₄TP) as the organic anode, the resulting K₄TP||PTCDI‐DAQ OPIBs with the electrolyte 1 m KPF₆ in DME realize a high energy density of maximum 295 Wh kg^?1_cathode (213 mAh g^?1_cathode × 1.38 V) and power density of 13 800 W Kg^?1_cathode (94 mAh g^?1 × 1.38 V @ 10 A g^?1) during the working voltage of 0.2–3.2 V. Meanwhile, K₄TP||PTCDI‐DAQ OPIBs fulfill the superlong lifespan with a stable discharge capacity of 62 mAh g^?1_cathode after 10 000 cycles and 40 mAh g^?1_cathode after 30 000 cycles (3 A g^?1). The integrated performance of PTCDI‐DAQ can currently defeat any cathode reported in K‐ion half/full cells.     

High performance Langmuir–Schaeffer film transistors based on air stable n-type diperylene bisimide

Diperylene Bisimide (DIPP–diPBI) mono- and/or multi-layer film using Langmuir–Schaeffer (LS) techniques has been fabricated and the OFET device performance based on the as-prepared LS film is investigated. The thickness of monolayer film is determined to be 2.3 nm by using atomic force microscopy, which is closely matched with the interplanar spacing estimated from the XRD spectra. The length of molecular long axis is measured to be 21.9 Å from the DFT optimized configuration, indicating that the long axis of molecule in LS film approximately stands upright on hydrophobic substrates. The absorption maximum at 417 nm shows a good linear corrleation with the layer number, proving the obtained films are deposited in a layer-by-layer fassion. The film with precision control of the long-range order and lateral packing density by LS deposition exhibits good electron injection properties and high FET device performance. The charge transport behavior is also investigated as a function of the layer number of LS film. The electron mobility gradually increases with the number of layers and saturates at a plateau with a mean value of 0.03 cm² V⁻¹ s⁻¹ in the atmosphere upon completion of the first eight layers. It is a direct evidence of physical size of charge transport layer. Furthermore, the fabricated FET device exhibits long-time stability in the air. The integration of LS method with air stability of the n-type compound affords an opportunity to explore solution-phase self-assembly and electronic devices fabrication with controllable molecular layers.     

Rigid‐rod polybenzoxazoles containing perylene bisimide: Synthesis,structures and photophysical properties

A novel perylene bisimide dye bearing carboxylphenylene substituents on the imide N atoms was synthesized and four conjugated copolymers containing different contents of perylene bisimide dye were synthesized via PPA/P₂O₅ copolymerization method. The structures of the four copolymers were characterized by FTIR, elementary analysis, ¹H‐NMR and XRD. The copolymers showed good thermal stabilities but poor solubilities due to the high rigidity of the backbone. The photophysical characteristics of the copolymers were investigated by UV‐Vis and PL spectra in solutions and films. Because of the conformational change of perylene bisimide chromophore, the absorptions of perylene bisimide core in copolymers showed a large blue‐shift (56 nm) compared to that of the perylene monomer. In PL experiments, when exciting the benzoxazole, an obvious fluorescent quenching was observed in all copolymers, which can be attributed to the energy transfer from benzoxazole units to perylene bisimide fragments and fluorescence quenching. With increasing perylene content, the copolymers turned to layered and friable. The XRD test showed that the interchain distances increased slightly with increasing perylene content. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Probing Bio–Nano Interactions between Blood Proteins and Monolayer‐Stabilized Graphene Sheets

Meeting proteins is regarded as the starting event for nanostructures to enter biological systems. Understanding their interactions is thus essential for a newly emerging field, nanomedicine. Chemically converted graphene (CCG) is a wonderful two‐dimesional (2D) material for nanomedecine, but its stability in biological environments is limited. Systematic probing on the binding of proteins to CCG is currently lacking. Herein, we report a comprehensive study on the interactions between blood proteins and stabilized CCG (sCCG). CCG nanosheets are functionalized by monolayers of perylene leading to significant improvement in their resistance to electrolyte salts and long‐term stability, but retain their core structural characteristics. Five types of model human blood proteins including human fibrinogen, γ‐globulin, bovine serum albumin (BSA), insulin, and histone are tested. The main drving forces for blood protein binding involve the π–π interacations between the π‐plane of sCCG and surface aromatic amonic acid (sAA) residues of proteins. Several key binding parameters including the binding amount, Hill coefficient, and binding constant are determined. Through a detailed analysis of key controlling factors, we conclude that the protein binding to sCCG is determined mainly by the protein size, the number, and the density of the sAA.