HYPERBRANCHED CONJUGATIVE MACROMOLECULES CONSTRUCTED FROM TRIPLE-BOND BUILDING BLOCKS

Polycyclotrimerization and polycoupling of acetylenic monomers respectively furnish hyperbranched polyarylenes and polyynes with high molecular weights （up to 1 × 10^6） in high yields （up to 99.9%）. The polymers possess low intrinsic viscosities and high thermal stabilities, losing little of their weights when heated to 〉 400℃. Upon pyrolysis at 〉 800℃, the polymers graphitize with high char yields （up to 86%）. Hyperbranched polyarylenes efficiently emit deep-blue to blue-green lights with fluorescence quantum yields up to 98% and strongly attenuate intense laser pulses with optical power-limiting performances superior to that of C60, a well-known optical limiter. Poly（alkenephenylenes）, poly（aroylarylenes） and polyynes are readily cross-linkable by UV irradiation, serving as excellent photoresist materials for the generation of patterns with nanometer resolution. Thin films of hyperbranched polyynes exhibit very high refractive indexes （n up to 1.86）. The internal and terminal acetylene moieties of the polyynes readily form complexes with cobalt carbonyls, which can be transformed into soft ferromagnetic ceramics with high magnetic susceptibilities （Ms up to ca. 118 emu/g） and near-zero magnetic losses.

SYNTHESIS AND PHOTOLUMINESCENCE OF AN ANTHRACENE-CONTAINING HYPERBRANCHED POLY(ARYLENEETHYNYLENE)

A hyperbranched poly（aryleneethynylene） containing anthracene chromophore was synthesized by palladiumcatalyzed cross-coupling reaction of 2,4,6-triiodophenyl 9-anthracenylcarboxylate with 9,9-bis[4-（2-propynyloxy）phenyl]- 9H-fluorene. The structure and properties of the polymer are characterized and evaluated by NMR, IR, UV, PL and TGA analyses. The polymer is soluble in common organic solvents, possesses high thermal stability （Td 〉 330℃）, and emits a strong blue light of 465 nm in both solution and solid states.

MECHANICAL PERTURBATION INDUCED MOLECULAR ALIGNMENTS IN A SIDE-CHAIN LIQUID CRYSTALLINE POLYACETYLENE, POLY{10-[4-(4'-METHOXYPHENOXY-CARBOML)PHENOXYCARBONYL]-1-DECYNE}

A new liquid crystalline polyacetylene containing a phenyl benzoate mesogen (5) is synthesized,whose mesomorphic properties are found to be easily 'tunab1e' by simple mechanical perturbation. Thepolymerization of 10- [ 4 - (4' -methoxyphenoxycarbonyl )phenoxycarbonyl] - 1 -decyne (4 ) in itiated by theWCl_6-Ph_4Sn/dioxane complex yields polymer 5 with a M_w of 28400. The molecular structure of 5 ischaracterized by NMR, IR, and UV spectroscopy and its liquid crystalline behavior is investigated by DSC,POM, and XRD analysis. Upon mechanical perturbation, 5 exhibits unusual agitation-induced high-strengthdisclinations, shear-induced inversion walls, and solidification-induced banded textures. Such phenomenahave been observed in the main-chain liquid crystalline polymers with rigid backbones, but have seldom beenreported for the side-chain liquid crystalline polymers with flexible backbones, suggesting that the rigidpolyacetylene backbone of 5 plays a constructive role in inducing the novel molecular alignments.

SYNTHESIS,HELICITY,AND BIOLOGICAL PROPERTIES OF MONOSACCHARIDE-CONTAININGPOLY(PHENYLACETYLENE)S

Poly（phenylacetylene）s beating monosaccharide pendant groups are synthesized in high yields by [Rh（nbd）Cl]2 catalyst. The polymers have high molecular weights and give satisfactory spectroscopic data corresponding to their molecular structures. They are thermally quite stable （≥ 300℃） and show strong circular dichroism signals in the visible spectral region owing to the helicity of the polyene backbone. The monosaccharide-containing polyacetylenes are cytophilic and can stimulate the growth of living cells.

CARBAZOLE-CONTAINING HYPERBRANCHED POLY(ARYLENEETHYNYLENE)S:SYNTHESIS,CHARACTERIZATION,ANDPROPERTIES

New hyperbranched poly（aryleneethynylene）s containing carbazole moieties are synthesized in high yields （up to 87%） by polycyclotrimerization of 3,6-bis（4-ethynylphenyl）-9-octylcarbazole and its copolymerization with 1-octyne catalyzed by CpCo（CO）2 in THF. The structures and properties of the polymers are characterized and evaluated by IR, NMR, TGA, UV, photoluminescence, and cyclic voltammetry analyses. All the polymers are soluble in common organic solvents and show outstanding thermal stability （≥ 430℃）. They graphitize in high yields （up to 79%） when pyrolyzed at 800℃. Upon photoexcitation, the polymers emit a strong deep blue light of ca. 400 nm with quantum yields larger than 60%.

PREPARATION OF SOLUBLE SUBSTITUTED POLYACETYLENE OPTICAL LIMITING MATERIAL

Two novel polyacetylenes bearing nonlinear optical chromophoric group poly（3-（4-[4-（n-butyloxy） phenylazophenyl]carbonyl）oxy-1-propyne） （poly（1a）） and poly（3-（4-[4-（n-heptyloxy）phenylazophenyl]carbonyl）-oxy-l- propyne） （poly（lb）） were synthesized with [Rh（nbd）Cl]2-EtaN as catalysts. These polyacetylenes are soluble by using an alkyl spacer and an alkyloxyl group as a substituent. They were characterized by FTIR, NMR, GPC and UV-Vis and their optical limiting and nonlinear optical properties were investigated using 8 ns pulse at 532 nm wavenumber. The results show that these soluble functional polyacetylenes possess optical limiting properties and large nonlinear optical properties and poly（1b） possesses better optical limiting and nonlinear optical properties than poly（ 1 a）.

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.

The specific detection of Cu(Ⅱ) using an AIE-active alanine ester

Cu（Ⅱ） detection is important because it plays crucial role in several biological processes and ecological systems.Fluorescent techniques have attracted more and more attention in Cu（Ⅱ） detection.In this report,we contribute a novel strategy to use fluorescence spectroscopy for Cu（Ⅱ） specific detection.The specificity relies on the fact that,of the many metal cations,only Cu（Ⅱ） can catalyze the hydrolyzation of a-amino acid ester.The novelty originates from the unique aggregation-induced emission（AIE） property of the fluorescent label.We designed a model a-amino acid ester（TPE-Ala） constructed with alanine and tetraphenylethene-functionalized methanol（TPE-methanol）.In comparison with the precursor TPE-Ala, TPE-methanol has lower solubility and is easy to form aggregates in water,thereby displaying a higher fluorescent response.Thus,the Cu（Ⅱ） catalyzed hydrolyzation can be monitored by recording the fluorescence enhancement and fluorescent detection Cu（Ⅱ） is rationally achieved.

Red fluorescent siloles with aggregation-enhanced emission characteristics

Aseries of new red fluorescent siloles consisting of a silole core and dimesitylboranyl substituent connected with a furan,thiophene,and selenophene bridges were synthesized and characterized.The optical properties,electronic structures,and electroluminescence (EL) performances were investigated.The emission wavelengths were red-shifted from the siloles with furan,to those with thiophene,and then selenophene.The thiophene,and selenophene-containing siloles,(MesB)_2DTTPS,and(MesB)_2DSTPS,showed the typical aggregation-enhanced emission (AEE) feature,while furan-containingone,(MesB)_2DFTPS,showed slight emission decrease as the aggregate formation.Theoretical calculations were carried out to explain the difference in the optical properties.Undoped OLEDs using these red siloles as light-emitting layers were fabricated.The device of (MesB)_2DTTPS exhibited the bestper formance.It radiated red ELemission at 589 nm,and afforded good maximum luminance,current,power,and external quantum efficiency of13300cdm^(-2),4.3cd A^(-1),2.9 lmW^(-1),and1.8%,respectively.