Theoretical study of low-lying excited states of molecular aggregates. I. Development of linear-scaling TD-DFT

The project aims to develop an integrated linear-scaling time-dependent density functional theory (TD-DFT) for studying low-lying excited states of luminescent molecular materials, especially those fluorescence and phosphorescence co-emitting systems. The central idea will be "from fragments to molecule" (FF2M). That is, the fragmental information will be employed to synthesize the molecular wave function, such that the locality (transferability) of the fragments (functional groups) is directly built into the algorithms. Both relativistic and spin-adapted open-shell TD-DFT will be considered. Use of the renormalized exciton method will also be made to further enhance the efficiency and accuracy of TD-DFT. Solvent effects are to be targeted with the fragment-based solvent model. It is expected that the integrated TD-DFT and program will be of great value in rational design of luminescent molecular materials.     

Influence of the alkyl side chain length on the room-temperature phosphorescence of organic copolymers

Pure organic room-temperature phosphorescence(RTP) materials have attracted wide attention owing to their excellent luminescent properties and great potential in various applications. In this work, iminostilbene and its analogues are applied to realize RTP emission by copolymerizing with acrylamide. It can be concluded that the growth of alkane chain in monomers can enhance the lifetime and photoluminescence quantum yield of RTP emission, and polymers with the larger conjugated structure of the ...     

Synthesis and characterization of a new dyestuff polymer soluble in alkaline aqueous media

Novel dyestuff polymers were successfully obtained through oxidative polymerization technique. The synthesized Schiff base and its polymer were soluble in alkaline＇aqueous medium and they have various colors in different solutions. Also, it can be said that the synthesized compounds are suitable as coloring agent （dyestuff） for textile applications. Fluorescence properties of the compounds were determined in DMF with different concentrations （mg/L）. Poly-tris（4- aminophenyl）methanol （P-TAPM） has quite high emission and excitation intensity values. Optical and electrochemical band gaps of the polymers were lower than those of the monomers indicating the more conjugated structure of the polymers. The oxidized states of the novel dyestuff compounds were examined by cyclic voltammetry （CV） technique. The solid state conductivity measurements showed that the synthesized polymers were semiconductors when exposed to the iodine vapour their conductivities could be increased. P-TAPM had the highest undoped conductivity. Thermal characterizations of the synthesized compounds were carried out by TG-DTA and DSC methods.     

Synthesis and Electrochemical Characterization of Azomethine Containing N-Ethylcarbazole Group

Conjugated aromatic azomethines containing a carbazole group were synthesized. Their structures have been confirmed by IR, MS and UV spectrometries. When iodine was used as the dope to the conjugated compounds, the electrical conductivities （EC） of the doped conjugated compounds were increased by several orders of magnitude. The thermal stability of these two compounds investigated by TGA shows a good result, which guarantees the correct result of EC when the compounds are heated. As can be seen from the CV characterization of the electrochemical properties of these two compounds, the azomethine diamine and p-aminophenyl-9-ethylcarbazolyl azomethine possess electrochemical activity, which arises from the heteroatom of molecules.     

Functional porous carbon-based composite electrode materials for lithium secondary batteries

The synthetic routes of porous carbons and the applications of the functional porous carbon-based composite electrode materials for lithium secondary batteries are reviewed. The synthetic methods have made great breakthroughs to control the pore size and volume, wall thickness, surface area, and connectivity of porous carbons, which result in the development of functional porous carbon-based composite electrode materials. The effects of porous carbons on the electrochemical properties are further discussed. The porous carbons as ideal matrixes to incorporate active materials make a great improvement on the electrochemical properties because of high surface area and pore volume, excellent electronic conductivity, and strong adsorption capacity. Large numbers of the composite electrode materials have been used for the devices of electrochemical energy conversion and storage, such as lithium-ion batteries (LIBs), Li-S batteries, and Li-O2 batteries. It is believed that functional porous carbon-based composite electrode materials will continuously contribute to the field of lithium secondary batteries.     

Size Effects on the Luminescence Properties of Polymer Nanowires简

Poly（3-（2-methoxyphenyl）thiophene） （PMP-Th） nanowires were fabricated using porous anodic alumina （PAA） as template through electrochemical polymerization by cyclic voltammetry. The control on the size of nanowires was confirmed by electron microscopy. The results indicated that the luminescence spectra of PMP-Th nanowires in PAA nanochannels were blue-shifted and emission intensity was enhanced compared to the emission of the PMP-Th film. Moreover, the luminescent spectra of PMP-Th nanowires were size dependent, which may result from the change in the degree of confinement of nanowires in PAA. F6rster energy transfer from PAA to PMP-Th molecules is considered to be responsible for the enhancement of luminescence from PMP-Th nanowires in PAA. The results show that the emission properties of polymers with nanostructures can be tuned by controlling their size.     

Hydride-Based Separation Materials for High Performance Liquid Chromatography and Open Tubular Capillary Electrochromatography

 Silica hydride is a recent development in chromatographic support materials for high performance liquid chromatography (HPLC) where hydride groups replace 95% of the silanols on the surface. This conversion changes many of the fundamental properties of the material as well as the bonded stationary phases that are the result of further chemical modification of the hydride surface. Some unique chromatographic properties of hydride-based phases are described as well as some general application areas where these bonded materials may be used in preference to or have advantages not available from typical stationary phases. The fabrication, properties and applications of etched chemically modified capillaries for electrophoretic analysis are also reviewed. It is shown that the etching process creates a surface that is fundamentally different than a bare fused silica capillary. The new surface matrix produces unique electroosmotic flow properties and is more compatible with basic and biological compounds. After chemical modification of the surface, the bonded organic moiety (stationary phase) contributes to the control of migration of solutes in the capillary. Both electrophoretic and chromatographic processes take place in the etched chemically modified capillaries leading to a variety of experimental variables that can be used to optimize separations. A number of examples of separations on these capillaries are described.     

Noncovalent conformational locks in organic semiconductors

Highly planar conformation is considered to be one of the most important properties for high performance organic semiconductors. Among all kinds strategies for designing highly performing materials, noncovalent conformational locks(NCLs)have been widely used to increase the planarity and rigidity for π-conjugated systems. This review summarizes π-conjugated small molecules and polymers by employing various NCLs for controlling molecular conformation in the past two years. The optoelectronic properties of the conjugated materials, together with their applications on organic field-effect transistors(OFETs)and organic photovoltaics(OPVs) are discussed. Besides, the outlook and challenges in this field are also presented. It is obvious that NCLs play an important role in the design and synthesis of high-performance organic semiconductors.     

CH2,NH,and O heteroatom substitution effects on the electronic,optical,and charge transport properties of a 2,1,3-benzothiadiazole-based derivative:Insights from theory

A set of CH2-,NH-,and O-substituted 2,1,3-benzothiadiazole(BTD)-based derivatives have been investigated theoretically in order to explore their electronic,optical,and charge transport properties.The calculation results show that the electronic and optical properties of the pristine molecule can be easily tuned through changing the S substituent in the central aromatic ring.Based on the calculated maximum emission wavelength,we predict that CH2-,NH-,and O-substituted BTD-based derivatives could be used as red,green,and orange light-emitting materials,respectively.After CH2-,NH-or O-substitution,the oscillator strengths of the emission spectra are enhanced with respect to that of the pristine molecule,implying that these compounds have larger fluorescence intensity.Finally,it can be deduced that CH2-,NH-,and O-substituted BTD-based derivatives may act as hole transport materials in organic light-emitting diodes.     

π-CONJUGATED OLIGOMERS IN SUPRAMOLECULAR CRYSTALS AND THEIR OPTOELECTRONIC FUNCTIONS

Functional organic molecular materials and conjugated oligomers or polymers now allow the low-cost fabrication of thin films for insertion into new generations of electronic and optoelectronic devices. The performance of these devices relies on the understanding and optimization of several complementary processes. Our goal is to discuss the relationship between the molecular stacking structures and their optoelectronic properties that are of importance in all these areas. The concept of intermolecular interaction should be taken here in the special sense that is inter-dipole coupling. Specifically, we will address the impact of inter-dipole interaction between adjacent molecules in aggregate state on the solid-state emission properties.     

Tuning the base properties of Mg–Al hydrotalcite catalysts using their memory effect

Herein,the relationship between the structure and base properties of Mg–Al hydrotalcite catalysts was comprehensively investigated in relation to heat treatment and rehydration processes,which are well known as memory effects of hydrotalcite.The structure of Mg–Al hydrotalcites changed from layered double hydroxide(LDH)to mixed metal oxide and subsequently to a spinel structure during heat treatment,and it was returned from mixed metal oxide to a LDH structure by rehydration.Based on various characterizations,we successfully proposed a detailed mechanism of memory effect.We also confirmed that the Mg–Al hydrotalcites had weak or strong base sites and that their base properties could be systematically tuned by heat treatment and rehydration.The prepared Mg–Al hydrotalcites were applied to a model reaction,isomerization of glucose to fructose,as base catalysts.Among the catalysts tested,the rehydrated Mg–Al hydrotalcite efficiently produced fructose due to its appropriate base and structure properties.We finally concluded that the base sites of Mg–Al hydrotalcites can be designed as desired by heat treatment and rehydration.Moreover,through systematic design of the base sites of Mg–Al hydrotalcites,these can be promising catalysts for various heterogeneous reactions over base catalysts,giving excellent catalytic performances.     

PHOTOCONDUCTIVITY STUDY OF NEW POLYACETYLENE DERIVATIVES WITH DIFFERENT SUBSTITUENTS

The photoconductivities of a series of novel polyacetylene derivatives （PAs） serving as charge generation materials in the single-layered photoreceptors were investigated using photoinduced xerographic discharge technique. It was found that the substitution can improve the photosensitivity of PAs by increasing the conjugation of π electrons. When the substituent is itself photoconductive, the photoconductivity becomes even higher. It can be concluded from cyclic voltammetry that when the HOMO level of the polymer is closer to that of the charge transport material, the photoconduction performance will be better.     

RECENT DEVELOPMENTS IN PHOTOINITIATED CROSSLINKING OF POLYETHYLENE AND ITS INDUSTRIAL APPLICATIONS

The recent developments in the photoinitiated cross-linking of polyethlene and the significant breakthrough of itsindustrial application are reviewed, The enhanced photo-initiation system, the dynamics of photoinitiated crosslinking, theoptimum conditions, the crystal morphological structures and related properties, and the photo- and thermo-oxidationstability of photocrosslinked polyethylene (XLPE) materials have been elucidated systematically. A new technique forproducing photocrosslinked XLPE-insulated wire and cable is described in detail. It can be expected that the fiture applications of photocrosslinking technique of polyolefins will be very promising.     

Luminescent nanoscale metal–organic frameworks for chemical sensing

Metal–organic frameworks(MOFs) are a fascinating class of crystalline materials constructed from selfassembly of metal cations/clusters and organic ligands. Both metal and organic components can be used to generate luminescence, and can further interact via antenna effect to increase the quantum yield,providing a versatile platform for chemical sensing based on luminescence emission. Moreover, MOFs can be miniaturized to nanometer scale to form nano-MOF(NMOF) materials, which exhibit many advantages over conventional bulk MOFs in terms of the facile tailorability of compositions, sizes and morphologies, the high dispersity in a wide variety of medium, and the intrinsic biocompatibility. This review will detail the development of NMOF materials as chemical sensors, including the synthetic methodologies for designing NMOF sensory materials, their luminescent properties and potential sensing applications.     

Highly Ordered Superlattices from Self-assembly of Fe3O4 Nanocrystals

The nano materials often exhibit very interesting electrical, optical, magnetic, and chemical properties, which can not be achieved by their bulk counterparts. The development of uniform nanometer sized particles has been intensively pursued because of their technological and fundamental scientific importance. It is significant that nanostructured materials can be controllably assembled into the required geometry onto substrates, becoming the basis of the next generation of components and devices. The development of new methods and strategies for organizing the nanoparticle basic building blocks into the desired structures is required. Superlattices made from these building blocks give us the opportunity to study not only the properties of the individual building blocks, but also collective effects. The superparamagnetic iron oxide nanocrystals（NCs） have been used in the fields of bio-medicine, ferrofluids, refrigeration system, catalysis,     

Improving the performance of arylamine-based hole transporting materials in perovskite solar cells:Extending π-conjugation length or increasing the number of side groups?

In this work, we prepared three simple arylamine-based hole transporting materials from commercially available starting materials. The effect of extending 7 r-conjugation length or increasing the number of side groups compared with reference compound on the photophysical, electrochemical, hole mobility properties and performance in perovskite solar cells were further studied. It is noted that these two kinds of molecular modifications can significantly lower the HOMO level and improve the hole mobility, thus improving the hole injection from valence band of perovskite. On the other hand, the compound with more side groups showed higher hole injection efficiency due to lower HOMO level and higher hole mobility compared with the compound with extending π-conjugation length. The perovskite solar cells with the modified molecules as hole transporting materials showed a higher efficiency of 15.40% and 16.95%,respectively, which is better than that of the reference compound(13.18%). Moreover, the compound with increasing number of side groups based devices showed comparable photovoltaic performance with that of conventional spiro-OMeTAD(16.87%).     

Influence of Surface Structure of Platinum Electrodes on Electrooxidation of CO

The oxidation of CO on platinum electrodes in an acid solution was studied with the conventional electro-chemical methods and the on-line electrochemical mass spectroscopy. It was found that this reaction is strongly determined by the surface morphology of platinum. The pretreatment of platinum electrodes can change the surface properties dramatically, in consequence it can improve the electrocatalytic activity towards the electrooxidation of CO. The existence of surface active sites on the roughened platinum electrodes can be used to explain its high electrocatalysis towards the oxidation of CO.     

Synthesis and Properties of Symmetrical Aryl Linked BODIPY Dyads

Three novel symmetrical 4.4＇-difluoro-4-bora-3a,4a-diaza-sindacene（BODIPY） derivatives were synthesized via a general and efficient protocol. These BODIPY dyads bear a diverse aryl linker bridge in the middle and two BODIPY units at the termini. The photophysical properties of these dyads were investigated by ultravioletvisible（UV-Vis） absorption and emission spectroscopy. And their electrochemical properties were studied by cyclic voltammetry. The absorption of these dyads showed slightly blue shift and the intramolecular charge transfer（ICT） state under,vent ultrafast direct surface crossing to the ground state with high degree of rotational freedom. The results will be useful for the further functionalization of these novel symmetrical BODIPY derivatives.     

SiO_x-based(0<x≤2) composites for lithium-ion batteries

Silicon(Si) materials as anode materials for applications in lithium-ion batteries(LIBs) have received increasing attention.Among the Si materials,the electrochemical properties of SiO_x-based(0x≤2)composites are the most prominent.However,due to the cycling stability of SiO_x being far from practical,there are some problems,such as Iow initial coulombic efficiency(ICE),obvious volume expansion and poor conductivity.Researchers in various countries have optimized the electrochemical properties of SiO_x-based composites by means of pore formation,surface modification,and the choice of constituents.In this review,SiO_x-based composites are classified into three categories based on the valency of Si(SiO_2 composites,SiO composites and SiO_x(0x2) composites).The synthesis,morphologies and electrochemical properties of the SiO_x-based composites that are applied in LIB are discussed.Finally,the prope rties of several common SiO_x-based composites are briefly compared and the challenges faced by SiO_x-based composites are highlight.     

Bowl-shaped conjugated polycycles

The conjugated polycycles show excellent optical and electrical properties that are suitable for application in various organic electronics.While most of attentions have been paid to polycycles having planar π-conjugated system,the curved polycycles seem amazing due to their unique physical and chemical features.The non-planar conjugated polycycles have been created with the geometries of bracelet,saddle,bowl,Mobius band,helicenes,etc.Among them,the bowl-shaped one is of growing interest owing to the multidiscipline applications such as synthetic intermediates for end-cap of carbon nanotube,coordination with metal ions,encapsulation of fullerenes,and fabrication of electronic devices.In this paper,we summarize the recent advances on the chemistry of the bowl-shaped conjugated polycycles,particularly on their synthesis and the further chemical modifications toward organic functional materials.