Two novel n‐type conjugated polymers based on perylene diimide (PDI), poly(PDI‐vinylene) (PDIV), and poly(PDI‐thienylene) (PDITh), have been designed and synthesized by the Stille coupling reaction. In comparison with the PDI monomer (compound M1), PDIV and PDITh films show a significantly broad absorption band from 380 to 720 nm, and a narrower bandgap of ≈1.71 and 1.74 eV, respectively. Cyclic voltammograms of the two polymers display a couple of reversible reduction/re‐oxidation (n‐doping/dedoping) peaks. The onset reduction (n‐doping) potentials of PDIV and PDITh are at −0.62 V and −0.66 V versus Ag/Ag+ respectively, which correspond to the electron affinities (EAs) of 4.09 eV for PDIV and 4.05 eV for PDITh. The EA values of the two polymers are the highest among the n‐type conjugated polymers reported to date. The results indicate that PDIV and PDITh could be used as polymer acceptors in all polymer solar cells.
Phosphorescent conjugated polymers consisting of alternating p‐phenylene‐ethynylene and ‘para‐’ or ‘meta‐type’ Pt(II)‐salphen luminophore units have been synthesized. Side‐arms bearing different substituents (n‐alkoxy and acetylated‐sugar) have afforded contrasting emission properties that are attributed to the polymer conformation, extent of π‐stacking interactions and differences in chemical structure. Intriguing selectivity in luminescent sensing of metal ions has been observed.
A conjugated polymer containing an electron donating backbone (triphenylamine) and an electron accepting side chain (cyanoacetic acid) with conjugated thiophene units as the linkers has been synthesized. Dye‐sensitized solar cells (DSSCs) are fabricated utilizing this material as the dye sensitizer, resulting a typical power conversion efficiency of 3.39% under AM 1.5 G illumination, which represents the highest efficiency for polymer dye‐sensitized DSSCs reported so far. The results show the good promise of conjugated polymers as sensitizers for DSSC applications.
Reactions between the ethylene groups in the backbone of conjugated polymers under UV illumination and heat treatment result in the cross‐linking of the main polymer chains. The cross‐linking leads to two simultaneous results in the polymer: excellent solvent resistance and increased bandgap. Using this reaction, three‐color polymer light‐emitting diodes (PLEDs) with a multi‐layer structure can be easily realized by a dry photo‐pattern in an active‐gas‐free environment. Multi‐layer blue devices with dramatically enhanced efficiency can also be achieved conveniently.
Summary: We investigate a series of glassy polymer actuators which are found to bend rapidly and reversibly in response to changes in the solvent environment. The actuators are based on hydrogen‐bonded liquid crystal networks, and bending motion is created using director profiles engineered to take advantage of the network swelling anisotropy. Strongly polar solvents easily swell the network, forcing bending in one direction, while the less polar solvents extract water to force bending in the opposite direction.
Shape variation of twisted configuration liquid crystal polymer films in acetone and water. 相似文献
Summary: A novel non‐aqueous emulsion system, consisting of cyclohexane as the continuous and acetonitrile as the dispersed phase, is described. Stabilization of the system can be achieved by using polyisoprene‐block‐poly(methyl methacrylate) copolymers as emulsifiers. The suitability of this system for performing water‐sensitive, catalytic, and oxidative polymerizations and polycondensations is demonstrated by the synthesis of poly(3,4‐ethylenedioxythiophene), poly(thiophene‐3‐yl‐acetic acid), and polyacetylene. In all cases spherical nanoparticles with diameters as small as 23 nm can be obtained.
A set of rigid π‐conjugated bis(terpyridine) macroligands with poly(ε‐caprolactone) (pCL) on their side chains was synthesized and investigated. The introduced pCL chains gave rise to enhanced processability and film‐forming properties of the materials. Blue photoluminescence with high quantum yields was observed in dilute solution and in the solid state, indicating that intermolecular aggregation of the π‐conjugated systems was effectively suppressed. The macroligands were further used for coordination with zinc(II) ions leading to new metallo‐polymers with high solubility, improved film‐forming behavior and promising photophysical properties with respect to potential OLED applications.
A ‘grafting‐from’ approach to synthesize microparticle‐supported conjugated polyelectrolyte brushes is presented. Poly(3‐bromohexylthiophene) is selectively grown from monodisperse organosilica microparticles by surface‐initiated Kumada catalyst‐transfer polycondensation (SI‐KCTP) and then ionizable amino groups are introduced by a two‐step polymer analogous transformation. Optical properties of the resulting microparticle‐supported conjugated polyelectrolyte brushes were found to be dependent on the surrounding chemical environment and thus the particles are promising materials for sensor applications.
Addition of commercially available 2‐isocyanatoethyl methacrylate to a water solution of potassium bisulfite unexpectedly yields an anionically charged hydrogel. Structural analysis shows the presence of sulfonato‐blocked isocyanates (with no detectable residual isocyanates), a full polymerization of the vinyl groups, and the appearance of urea functional groups. A mechanism is proposed to explain the gel formation, based on a combination of bisulfite‐initiated free‐radical polymerization, crosslinking by urea bridge formation, and addition of bisulfite ions to isocyanate groups. Some basic physical properties (TGA, swelling) of the gel are presented.
The synthesis of cationic mono‐(6‐O‐(1‐vinylimidazolium))‐ß‐cyclodextrin with toluenesulfonate as the corresponding anion is described. Free‐radical copolymerization of the resulting host–guest complex with N‐isopropylacrylamide or N,N‐diethylacrylamide yielded copolymers showing a temperature‐controlled solubility window in water. The impact of different anionic guests and salt concentrations on solubility behavior was investigated via turbidity measurements.
Novel glucosamine hydrochloride functionalized water‐soluble conjugated polyfluorene was easily synthesized through Cu(I)‐catalyzed azide/alkyne “click” ligation and Suzuki coupling polymerization. The water‐solubility and biocompatibility of the polymer were improved after grafting glucosamine hydrochloride to the side chains of the conjugated polymer. As a fluorescent model system of chitosan, its interaction with single‐stranded DNA was studied by spectrofluorometric titration.
A folate‐conjugated copolymer PEG‐PLA‐PLL/folate was synthesized and mixed with pure PEG‐PLA‐PLL and a fluorescent model drug mFITC to prepare folate‐conjugated micelles. The distribution of micelles was studied on cancer‐cell‐bearing mice via frozen slicing. The r e sults show that mFITC is successfully encapsulated into folate(+) and folate(?)micelles; PEG‐PLA‐PLL micelles the latter can be internalized by both HeLa and CHO cells without selectivity due to their cationic surface charges, while folate(+)micelles exhibit more preferential endocytosis by HeLa cells than by CHO cells. The folate(?)micelles showed retention in both organs and tumors. The folate(+)micelles are a promising active targeting drug delivery system for FR over‐expressing cells and they accumulate in tumor beds.
Based on their rigid‐rod structure all‐conjugated, rod‐rod block copolymers show a preferred tendency to self‐assemble into low‐curvature vesicular or lamellar nanostructures independent from their specific chemical structure and composition. This unique and attractive behaviour is clearly illustrated in a few examples of such all‐conjugated block copolymers. The resulting nanostructured heteromaterials may find applications in electronic devices or artificial membranes.
Polycondensation of 1‐(2‐pyrimidinyl)pyrrole with 2,7‐dibromo‐9,9‐dioctylfluorene via Ru‐catalyzed direct arylation gives the corresponding conjugated polymer with a molecular weight of 19 800 in 86% yield. The introduction of directing group, 2‐pyrimidinyl substituent, into the pyrrole monomer induces ortho‐metalation and provides the site‐selective direct arylation polycondensation at the α‐position of pyrrole unit without the protection of β‐position. The removal of 2‐pyrimidinyl substituent on the pyrrole unit proceeds efficiently and results in the enhancement of coplanarity along the main chain of the polymer.
The complexation of bile acids with various solvated polycations was studied. A one‐to‐one complex was precipitated when an aqueous solution of cholic acid sodium salt (CA) was mixed with aqueous solutions of 3,3‐ionene and grew to form crystals with needle‐like morphology, 3 millimeters in length. Hydrogen bonding of hydroxyls at the steroid face and the spacing between cationic sites of polycations were crucial for the formation of the giant needle.
Crossed polarizing microscopic photograph of the complex composed of cholic acid sodium salt and 3,3‐ionene. 相似文献
The mode of packing and the adjacent re‐entry folds of chains of syndiotactic 1,2‐poly(1,3‐butadiene) have been studied by molecular mechanics calculations with the use of various sets of potential functions. The results of the packing analysis indicate that the crystal grows preferentially along the [100] and [110] directions. Models of fold have been built up on an infinite ab surface completely covered by adjacent re‐entry folds in the (100) and (110) planes. The results of energy minimizations show that several almost isoenergetic folds, constituted by four monomeric units, can be realized in the (100) planes, while the fold in the (110) planes has higher energy. The calculated value of the work of fold is in satisfactory agreement with that derived by crystallization kinetics reported in literature.
The electrical conductivity of composites of exfoliated graphite nanoplatelets (GNPs), including bromine‐doped GNP, and conjugated polyacrylonitrile has been investigated. The focal point is the dual nature of the graphite nanoparticles, which exhibit both intrinsic electrical conductivity and doping capability of semi‐conductive polymers such as conjugated polyacrylonitrile to form charge‐transfer complexes. The conductivity is particularly enhanced in conjugated polyacrylonitrile composites (e.g., with 6 wt.‐% graphite nanoplatelets) where the value rises from 1 × 10−10 to 2 × 10−3 S · cm−1, which reflects jointly the conductivity of the doped semi‐conductive polymer together with the percolation‐based conductivity of the particles.
The various end‐to‐end distances of four‐junction polymers are investigated. The sizes of the different kinds of equal length branches and the backbone of two different polymers, with either nine or eleven branches, are estimated by means of both renormalization‐group and MC calculations. The comparisons of first‐order ε = 4 − d predictions with the MC results are satisfactory. The same trends are present in both techniques. The excluded‐volume interactions from additional branches further expand the various parts of the chains so that internal branches are larger than external ones. The branch ratios in the eleven‐branch case are expanded even more than the corresponding ratios of the nine‐branch polymer.
Blue‐light‐emitting 2,7‐carbazole‐based conjugated copolymers have been prepared by Yamamoto or Suzuki cross‐coupling reactions. By introducing highly substituted aromatic comonomers, fully soluble high‐molecular‐weight copolymers have been obtained. Moreover, these amorphous polymeric materials exhibit good thermal stability and interesting redox properties. All these features make these new conjugated polymers highly promising for the development of single‐polymer‐layer blue‐light‐emitting diodes.
Crystallization of poly(2‐isobutyl‐2‐oxazoline) and poly(2‐nonyl‐2‐oxazoline) is found to occur by room temperature annealing below the upper critical solution temperature in ethanol–water solvent mixtures. Both polymers produce similar self‐assembled structures (see image), resembling the previously reported crystalline hierarchical structures obtained from hot aqueous poly(2‐isopropyl‐2‐oxazoline) solutions above the lower critical solution temperature. These observations suggest that the crystallization induced self‐assembly process is a rather general phenomenon occurring for semicrystalline polymers in liquid–liquid two phase systems.
