苯并菲盘状液晶的合成、亲氟效应及分子对称性对介晶性的影响

New symmetrical and asymmetrical triphenylene-containing discotic liquid crystals with two different peripheral alkyl chains, known as sym-TP(OC6H13)3(OR)3 and asym-TP(OC6H13)3(OR)3, were synthesized. Their thermotropic liquid crystal properties were investigated through polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. The asyrranetdcal discogens are 2,6,11-rialkoxy-3,7,10-trihexyloxytriphenylenes, with the alkyl chain carbon numbers varying from 3-10, 12, and 14, while the symmetrical compounds are 2,6,10-trialkyloxy-3,7,11-trihexyloxytriphenylene. Two fluoroalkoxy substituted triphenylene discogens, 2,6,10-td(4,4,4-trifluorobutoxy)-3,7,11-trihexyloxytriphenylene and its asymmetrical isomer 2,6,11-tri(4,4,4-trifluorobutoxy)-3,7,10-trihexyloxytdphenylene were prepared. These two compounds show higher melting and clearing points than their alkoxy analogs, which implies that fluorophilic effect exists in the formation and stabilization of discotic columnar mesophase. The triphenylene derivatives TP(OC6H13)3(OR)3 with two different peripheral chains, symmetrically or asymmetrically attached on triphenylene cores, have lower melting points and clearing points than those of the higher symmetrical compounds TP(OR)6 with the same total chain carbon numbers. The mixed-chain-triphenylenes with longer alkoxy chains (n=9,10,12,14) show columnarmesophase at room temperature.     

Synthesis of unsymmetric triphenylene discotic liquid crystals with a semi-fluorinated chain and the influence of fluorophobic effect on mesogenic behavior

The fluorophobic effect of the semi-fluorinated chain of discotic molecules efficiently improves the stability of columnar mesophase.Low symmetric discogens exhibit decreased melting points and wide mesophase ranges.A series of triphenylene derivatives 1,C18H6(OCnH2n+1)4(OMe)(O2CC2H4C6F13),and their hydrocarbon analogues 2,C18H6(OCnH2n+1)4(OMe)(O2CC8H17),n = 4―8,were synthesized for the investigation of the influence of semi-fluorinated peripheral chain and molecular symmetry on mesomorphism.The structures ...     

新的混合柔链苯并菲盘状液晶：分子对称性与宽温柱状介晶相

A series of new trialkoxytrialkanoyloxytriphenylene TP（OCnH2n＋1）3（OCOCmH2m＋1）3 （5a-5e） （n =m＋1 =4- 8） discotic liquid crystals were prepared and their mesomorphic properties were investigated using differential scanning calorimetry （DSC） and polarizing optical microscopy （POM）. The symmetrical and shorter chain triphenylenes display higher melting points and clearing points, more highly ordered and stable columnar mesophase than the asymmetrical and longer chain triphenylenes respectively.     

Liquid crystal character controlled by complementary discotic molecules mixtures: Columnar stacking type and mesophase temperature range

In this work, the mesophase properties were tuned via mixing two discotic molecules with structural complementarity. Compared with the liquid crystalline hexakis(n-hexyloxy)triphenylene(H6TP)materials(columnar hexagonal phase from 53 8C to 91 8C), mesophase types as well as phase transition temperatures varied with the introduction of crystalline hexaazatriphenylene derivative(PBH)molecules. The introduction of less than 33% amount of PBH disrupted the columnar hexagonal phase formed by H6 TP remarkably, followed by the decreased clearing temperatures of liquid crystals. As the PBH amount was further increased, the destroyed columnar hexagonal phase was turned into the columnar rectangular phase, in which H6 TP and PBH molecules together formed the columnar mesophase. The formation of new mesophase contributed to the enlarged mesophase temperature(from44 8C to 144 8C). We speculated that the alkyl chains interaction induced by the PBH component competed with the strong p–p stacking between H6 TP molecules, thus altering the liquid crystalline properties including mesophase types and phase transition temperatures.     

Synthesis and mesomorphism of diacetylene-bridged triphenylene discotic liquid crystal dimers

Connecting two discotic mesogens via a spacer not only stabilizes the columnar mesophase but also leads to the formation of glass columnar phase, and therefore improves the physical properties of discotic liquid crystals as organic semiconductor. Here, we report the synthesis of eight diacetylene-bridged triphenylene discotic liquid crystal dimers, [C18H6(OCnH2n+1)4(OMe)O2C-C8H16-C≡≡ C-]2, 3(n), (n = 4-8), [C18H6(OC6H13)5O2C-C8H16-C≡≡ C-]2, 6 and [C18H6(OC6H13)5O-(CH2)m-C≡≡ C-]2, 8(m), (m = 1, 3) by Eglinto...     

SYNTHESIS AND PROPERITIES OF SHISH-KEBAB-TYPE LIQUID CRYSTALLINE POLY（p-PHENYLENE）S

Abstract The novel shish-kebab-type liquid crystalline poly（p-phenylene）s were synthesized through Suzuki coupling reaction from 2,5-bis[（4-n-alkoxyl）benzoyloxy]1,4-dibromobenzene （monomer 1） and 1,4-benzenediboronic acid bistrimethylene cyclic ester （monomer 2）. Their structure and properties were characterized by GPC, DSC, X-ray diffraction and polarizing optical microscope （POM）. It was found that the polymers turned to liquid crystalline phase above their melting point. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The mesophase was identified by X-ray diffraction method. The polymers could dissolve in common organic solvents and show strong blue fluorescence. The maximum absorption bands of polymers prepared from annealed films have large red-shift due to the spontaneous orientation of the liquid crystalline side chains. The same phenomena were also observed in the fluorescence spectra.     

Synthesis and properties of polyfluorene copolymers bearing thiophene and porphyrin

To search for more wider absorption and higher charge carriers mobilities materials of polymer solar cell, a series of soluble alternating polyfluorene copolymers were synthesized by palladium-catalyzed Suzuki coupling reaction. Their structures were determined by 1H NMR, IR and UV-vis. And their UV-vis absorption spectra indicated that they had strong absorption over 600 nm spectral range and nearly cover 400-700 nm visible region. The band gaps of copolymers calculated according to cyclic voltammetry （CV） were between 1.96 and 2.03 eV. Polymer：TiO2 bulk-heterojunction films were made from mixtures of polymer and titanium isopropoxide, a precursor for TiO2, via hydrolysis in air overnight. The photoluminescence at 380-800 nm of the blend film of PT-TPP20 （5 mg/mL）：Ti（OC3H7）4 （80 μL/mL） （20% volume fraction） was significantly quenched in the 50% Ti（OC3H7）4 blend film, indicating that rapid and efficient separation of photoinduced electron-hole pairs.     

The Reaction of Molybdenum with 2,3-Dihydroxynaphthalene

[H2N（CH2）3NH312[MoO2（C10H6O2）2] （1） was synthesized by the 2,3-dihydroxynaphthalene in the mixed solvent of CH3OH, CH3CN reaction of （n-Bu4N）4[Mo8O26] with and 1,3-propanediarnine. （C5HllN2）2- [HeN（CH2）3NH2][MoO2（CloH6O2）2] （2） was obtained by the reaction of Na2MoO4.2H20 with 2,3-dihydroxynaphthalene in the same solvent above. Both of the complexes possess complex anion [Mo（VI）O2（OC10H6O）2]^2- which shows pseudo-octahedrally coordinated fashion, while the counterions are two protonated 1,3-propanediamine in complex 1 and （CsH11N2）^＋ in complex 2. （C5H11N2）＋ is the byproduct of reaction 2, which results from combination of acetonitrile with 1,3-propanediamine. Packing diagrams of the two complexes are also different. There is anti-parallel-aligned-double-meso-bilayer unit in complex 1. However there are four chiral anions arranged in anticlockwise orientation in complex 2.     

Synthesis, Spectroscopic and Electrochemical Investigations of Two vic-Dioximes and Their Mononuclear Ni（Ⅱ）, Cu（Ⅱ） and Co（Ⅱ） Metal Complexes Containing Morpholine Group

Two vic-dioxime ligands （LxH2） containing morpholine group have been synthesized from 4-[2-（dimethylaminoethyl）] morpholine with anti-phenylchloroglyoxime or anti-monochloroglyoxime in absolute THF at -15 ℃. Reaction of two vic-dioxime ligands with MCl2·nH2O （M： Ni, Cu or Co and n=2 or 6） salts in 1 ： 2 molar ratio afforded metal complexes of type [M（LxH）2] or [M（LxH）2·2H2O]. All of metal complexes are non-electrolytes as shown by their molar conductivities （Am） in DMF （dimethyl formamide） at 10^-3 mol·L^-1. Structures of the ligands and metal complexes have been solved by elemental analyses, FT-IR, UV-Vis, ^1H NMR and ^13C NMR, magnetic susceptibility measurements, molar conductivity measurements. Furthermore, redox properties of the metal complexes were investigated by cyclic voltammetry.     

Formation of Poly（L-lactide） Mesophase and Its Chain Mobility Dependent Kinetics

In the present work, the PLLA mesophase formation and its kinetics at the advent of a chain mobility accelerator （polyethylene glycol （PEG）） are investigated by wide angle X-ray diffraction （WAXD） and time-resolved Fourier transform infrared spectroscopy （FTIR）. It is interestingly found that the presence of PEG could accelerate the formation of PLLA mesophase notably due to the enhanced chain mobility, giving rise to a substantially reduced half time （t0.5） of PLLA mesophase formation from 129 min to 8 min. The Avrami exponents （n） for the kinetics of mesophase formation are -0.5 for neat PLLA and 1 for PLLA/PEG, respectively, indicating that 1D-rod growth through heterogeneous nucleation occurs during formation of PLLA mesophase. Tensile testing demonstrates that PLLA mesophase could increase the tensile strength and modulus but decrease the elongation at break.     

Partial Oxidation of Butane to Syngas over Nickel Supported Catalysts Modified by Alkali Metal Oxide and Rare-Earth Metal Oxide

There are abundant supplies of mixture gases containing CH4, C2H6, C3H8 and C4H10, etc. from FCC (Fluidized Catalytic Cracking) tail gas, refinery gas, etc. Commonly, the mixture gases are primarily combusted to carbon dioxide because the complete separation of CH4, C2H6, C3H8 and C4H10, respectively, from the mixture gases may not be economical. Provided that syngas (CO+H2) could be produced from the mixture gases over nickel supported catalysts with high selectivity and conversion,…     

2-(对烷氧基苯甲酸酯基或对烷氧基苯丙烯酸酯基)-5-氧-2,5-二氢呋喃化合物的合成与液晶性质研究

Two series of p-alkoxybenzoates Ia-If and p-alkoxycinnamates IIa-IIf, each species beating one terminal furanone, have been synthesized and characterized by IR, ^13C NMR, ^1H NMR, MS spectra and elemental analysis. The mesogenic properties of both series of furanones have been studied by polarizing optical microscopy and differential scanning calorimetry （DSC）. The relationship between structures and mesogenic properties was discussed. The results show that the increased alkoxy chain length （C7-C12） and the bridging groups between the benzene ring and the furanone ring affected the mesomorphic properties greatly, and the two series of furanones might display monotropic or enantiotropic nematic （N） or semetic C （SmC） mesophases and different mesomorpic phase temperature ranges corresponding to different carbon chain length.     

Synthesis,Crystal Structure,Vibrational Spectroscopy and Thermal Behavior of the First Alkali Metal Hydrated Hexaborate： K2[B6O9（OH）2]

New hydrated potassium hexaborate K2[B6O9（OH）2] has been synthesized under mild solvothermal conditions. The structure was determined by single-crystal X-ray diffraction and further characterized by FT-IR, Rarnan spectra and DTA-TG. It crystallizes in the monoclinic system with space group P21/n, a=0.9036（2） nm, b=0.66052（18） nm, c=1.5997（4） nm, β=91.862（4）°, V=0.9543（4） nm^3 and Z=4. Its crystal structure consists of K-O polyhedra and 1-D stepped polyborate chains constructed by new [B6O9（OH）2]2- fundamental building blocks. 1-D polyborate chains contain 3,8-membered boron rings. Adjacent chains are further linked via H-bonding interactions into 2-D layers. The K^＋ cations reside not only between the layers but also in the 8-membered boron rings of the chains, compensating the negative charges of the borate chains and holding the layers together into the 3-D structure through bonding with oxygen atoms of the chains.     

1,2-二芳基乙炔的简便合成及其结构与性能关系研究

1,2-Diarylacetylenes have been synthesized by a facile method consisting of an addition of diaryl ketone with acetyl chloride and the elimination of resultant ethene chloride. Correlation between physical properties and structure of the 1,2-diarylacetylene has been studied by differential scanning calorimeter （DSC）, refractor and electro-optical parameter test instrument. The results show that birefringence was increased with inserting cyclohexyl into the skeleton, but mesophase range, melting and clearing points were reduced with introducing the ethylene bridge in the molecule, and birefringence, viscosity, clearing point and mesophase range could all be decreased with perfluoro alkyl/alkoxyl terminal instead of alkyl/alkoxyl moiety.     

Multiple Effects Tailoring the Self-organization Behaviors of Triphenylene Side-chain Liquid Crystalline Polymers via Changing the Spacer Length

Long-alkyl tail triphenylene(TP) side-chain liquid crystalline polymers(SCLCPs) with different spacer length(P-m-TP,m =2,3,4,6,8,which is the number of carbon atom in the flexible alkyl spacers) have been successfully synthesized via free radical polymerization.The differential scanning calorimetry(DSC),polarized light microscopy(POM),ultraviolet-visible spectroscopy(UVVis),wide-angle X-ray diffraction(WAXD) and small-angle X-ray scattering(SAXS) measurements were performed to investigate the influence of multiple effects on the self-organization behaviors of P-m-TP,including steric effect,decoupling effect and π-π stacking effect.The experimental results revealed that P-m-TP(m = 2,3,4) formed the columnar phase which was developed by the TP moieties and the main chain as a whole,suggesting that the side-chains had strong steric effect even though the number of spacer length(m)exceeded 4.In addition,the clearing points(Tis) of the polymers were above 300 °C.When m = 6 and 8,the polymers displayed hexagonal columnar phase and exhibited the low Tis(91 and 80 °C respectively),originating from the self-assembly of triphenylene due to the decoupling effect and π-π stacking effect.This work offers a viable and inspiring pathway to control the phase transition temperature and phase structure of TP SCLCPs via simply tailoring the spacer length and increasing the alkyl tail length of TP.     

Size Dependence of Electronic Excitation Energy in Linear C_(2n)H and C_(2n-1)N

IntroductionCarbon chains are among the most attractivecandidates as the carriers of the diffuse interstellarbands ( DIBs) [1] .To detect the carbon chains indark clouds and carbon stars[2 ] ,itis very importantto understand their electronic spectra.Maier andhis coworkers have measured the polyacetylenicradicals C2 n H( n=1— 4) and C2 n-1H( n=2— 6) bythe rotational spectroscopy[3 ,4] and the species n≤ 4have been detected in dark interstellar clouds[5,6] .In neon matrices,the B2 Π← X2…     

Crystal Structure of an Octanuclear Sandwich Cluster of Silver（I） and 4,4＇-Bis（2,5-dimethylstyryl）biphenyl

Reaction of the oligo（phenylenevinylene） 4,4＇-bis（2,5-dimethylstyryl）biphenyl （bdb） with CF3CO2Ag in benzene gave a novel octanuclear sandwich cluster [Ags（bdb）2（C6H6）2（CF3CO2）8]·2C6H6 （1）. The clusters are packed on each other through strong n-n interactions to form ^1D ＇brick＇ chains, between which the solvated benzene molecules are located. TG analysis showed that cluster 1 could completely liberate the guest benzene molecules at 105℃ and the coordinated benzene molecules at 180 ℃. In solid state, cluster 1 exhibits fluorescence, and the emission band is red-shifted compared with that of free ligand bdb.     

Preparation of Polystryenylphosphonous Acid of Low Polymerization Degree and Influence of Initiators upon the Free Radical Reaction Mechanism

The polystyrenylphosphonous acid (PSPA) of low polymerization degress was prepared with one step reaction. The reaction mechanism was changed with different initiators. For the reaction with AIBN or BPO as the initiator, therer are 2 or 3 serives of radical reaction chains and 5 or 9 series of polystyrenyl products. The main products are PSPA without or with the fragment of the initiator H[CH(C6H5)-CH2]n-PO2H2 and C6H5CO2-[CH2CH(C6H5)]n-PO2H2 respectively.     

Syntheses, Crystal Structures, and Properties of Two Mixed-ligand Coordination Polymers： [Zn（bdc）（1,3-bimb）]_n and {[Mn_2（ox）_2（1,3,5-tib）_（4/3）]·4H_2O}_n

Two new coordination polymers,[Zn（bdc）（1,3-bimb）]n（1） and {[Mn2（ox）2（1,3,5tib）4/3]·4H2O}n（2）（H2ox = oxalic acid,H2bdc = terephthalic acid,1,3-bimb = 1,3-bis（imidazol-1ylmethyl）benzene,1,3,5-tib = 1,3,5-tri（imidazol-1-yl）benzene）,were synthesized and characterized by elemental analysis,IR,powder X-ray diffraction（PXRD）,and thermogravimetric（TG） analyses.X-ray diffracation analysis reveals that two kinds of zigzag chains [Zn（bdc）]n and [Zn（1,3-bimb）]n in compound 1 are interweaved to form a 3D 4-fold interpenetrated 66-dia framework.In compound 2,Mn（1） and Mn（2） are linked via 1,3,5-tib ligands to form two different nets of [Mn6（1,3,5-tib）6 ]n along the ab plane with inner-or outer-shape N–Mn–N angles,which are connected by 1D infinite [Mn2（ox）2 ]n chains via Mn–O bonds to result in a（3,3,3,4,4）-connected（4·8·10）3（4·82）3（4·83·102）6（82·104·3）3（83）4 topology.Moreover,the photoluminescence of 1 has been investigated.The crystal of 1 crystallizes in orthorhombic,space group Pna2 with a = 13.2267（6）,b = 9.1717（4）,c = 17.4492（8）,V = 2116.79（16）3,Z = 4,C22 H18N4O4 Zn,Mr = 467.77,Dc = 1.468 g/cm3,F（000） = 960 and μ（MoKα） = 1.197 mm-1.The final R = 0.0280 and wR = 0.0618 for 3695 observed reflections with I 2（I） and R = 0.0389 and wR = 0.0653 for all data.The crystal of 2 crystallizes in rhombohedral,space group R-3 with a = 22.080（8）,c = 31.19（2）,V = 13167（11） 3,Z = 18,C24 H25 Mn2 N8 O13,Mr = 743.40,Dc = 1.688 g/cm3,F（000） = 6822 and μ（MoKα） = 0.945 mm-1.The final R = 0.0429 and wR = 0.1035 for 5160 observed reflections with I 2（I） and R = 0.0824 and wR = 0.1244 for all data.     

Synthesis,structure and magnetic properties of manganese（Ⅱ） coordination polymer with azido and zwitterionic dicarboxylate ligand

A coordination polymer formulated as {[Mn2L（N3）4]·2H2O）n（1） [L = 1,4-bis（pyridinil-3-carboxylato）-1,4- dimethylbenzene] was synthesized and structurally and magnetically characterized. The uniform Mn（Ⅱ） chains with mixed （μ-EO-N3）2（μ-COO） triple bridges （EO = end-on） are linked by L ligands to generate a 2-fold interpenetrating 3D framework. Meanwhile, magnetism analysis reveals antiferromagnetic coupling for 1.