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1.
Aggregation‐induced emission (AIE), in which the luminophores are highly emissive in aggregate state, is one of the most unique photophysical phenomena and has shown interesting applications in many areas. The immobilization of AIE luminogens (AIEgens) into metal‐organic frameworks (MOFs), which are inorganic‐organic hybrid porous materials with tunable and predictable structures, has been investigated over the past few years. These well‐defined porous frameworks cannot only provide an ideal platform for studying the mechanism of AIE phenomenon in solid state, but also show potential applications from sensing to white light‐emitting diodes. In this highlight, we will summarize the recent progress of AIEgens‐based MOFs, including ligand design, emission behavior, and applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1809–1817  相似文献   

2.
Emissive β‐diketones (bdks) and difluoroboron complexes (BF2bdks) show multi‐stimuli responsive luminescence in both solution and the solid state. A series of bdk ligands and boron coordinated dyes were synthesized with different cyclic amine substituents in the 4‐position to explore ring size effects on various luminescent properties, including solvatochromism, viscochromism, aggregation‐induced emission (AIE), mechanochromic luminescence (ML) and halochromism. Red‐shifted absorption and emission were observed in CH2Cl2 for both bdk ligands and boron dyes with increasing substituent ring size. The compounds displayed bathochromic emission in more polar solvents, and higher fluorescence intensity in more viscous media. The AIE compounds exhibited enhanced emission when aggregated. For solid‐state properties, a large emission wavelength shift was shown for the piperidine substituted bdk after melt quenching on weighing paper. Large blue‐shifted emissions were observed in all the boron dye spin cast films after trifluoroacetic acid vapor annealing, and the original emissions were partially recovered after triethylamine vapor treatment.  相似文献   

3.
A series of main‐chain metallopolymers ( P1–P10 ) was prepared by the self‐assembly of rigid‐linear π‐conjugated bis(terpyridine) monomers ( 1–10 ) with ZnII ions and was fully characterized. The polymerization was additionally confirmed by UV/vis titration experiments. A strong increase in viscosities (around 1.6 times) relative to those of the monomer solutions was found. The thermal stability of P1–P10 compared with that of 1–10 was enhanced as a result of the metallopolymerization. The electro‐optical properties of the materials were investigated in detail. Tuning of the electrochemical and photophysical properties was enabled; thus, bright purple to green photoluminescent (PL) emission (PL quantum yields of 0.12–0.81) for P1–P10 was observed in solution with the emission color strongly depending on the nature of the π‐conjugated bis(terpyridine) system. Thin homogeneous films of P6 were prepared by solution processing, that is, spin‐coating and inkjet‐printing, and exhibited intense yellow PL emission in the solid state. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4083–4098, 2009  相似文献   

4.
Four novel poly(aryl ether)s ( P1 – P4 ) consisting of alternate isolated electron‐transporting (3,3″′‐bis‐trifluoromethyl‐p‐quaterphenyl for P1 , P3 or 3,3″′‐dicyano‐p‐quaterphenyl for P2 , P4 ) and hole‐transporting fluorophores [N‐(2‐ethylhexyl)‐3,6‐bis(styryl)carbazole for P1 , P2 or 9,9‐dihexyl‐2,7‐bis(styryl)fluorene for P3 , P4 ] were synthesized and characterized. These poly(aryl ether)s can be dissolved in organic solvents and exhibited good thermal stability with 5% weight‐loss temperature above 500 °C in nitrogen atmosphere. The photoluminescent (PL) spectra of the films of these polymers showed maximum peaks at around 442–452 nm. The PL spectral results revealed that the emission of polymers was dominated by the fluorophores with longer emissive wavelength via the energy transfer from p‐quaterphenyl to 3,6‐bis(styryl)carbazole or 2,7‐bis(styryl)fluorene segments. Therefore, the p‐quaterphenyl segments function only as the electron‐transporting/hole‐blocking units in these polymers, and the other segments are the emissive centers and hole‐transporting units. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital energy levels of these polymers were measured by cyclic voltammetry. The electron‐donating nitrogen atom on carbazole resulted in the higher HOMO energy levels of P1 and P2 than those of P3 and P4 . The single‐layer light‐emitting diodes (LED) of Al/poly(aryl ether)s ( P1 – P4 )/ITO glass were fabricated. P1 , P2 , and P4 revealed blue electroluminescence, but P3 emitted yellow light as a result of the excimer emission. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2215–2224, 2002  相似文献   

5.
The steady‐state and time‐resolved photoluminescence (PL), electrochemical behavior, and electroluminescence (EL) of didodecyloxy poly(p‐phenylenevinylene)‐based polymers that contained along the backbone structure 1,3,5‐triphenylbenzene (PC) or 2,4,6‐triphenylpyridine (PN) were studied. An intensive green PL broad‐band emission with maxima at 516 and 527 nm was observed from thin films of PC and PN polymers, respectively, redshifted in comparison with the PL emission spectra measured in tetrahydrofuran solutions. The PL decay dynamics revealed the existence of more than one excited species, and the decay curves were best described by three‐term exponential functions with a dominant lifetime of about 1 ns. The results of time‐resolved PL and steady‐state PL studies indicated excimer or aggregate formation. Both polymers oxidized irreversibly. A quasireversible reduction was observed in the PN polymer, whereas the PC polymer reduced irreversibly. For PC, slightly higher values of the ionization potential (EIP) and electron affinity (EA) were found (EIP = 5.52 eV, EA = 2.85 eV) than those for PN (EIP = 5.37 eV, EA = 2.77 eV). Light‐emitting devices with indium tin oxide hole‐injecting and aluminum electron‐injecting electrodes were prepared and studied. They emitted green light, and their EL spectra were similar to those of PL thin films. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 524–533, 2006  相似文献   

6.
We report the optical and electroluminescent properties of four novel poly(aryl ether)s ( P1 – P4 ) consisting of alternate isolated hole‐transporting [carbazole or 3,6‐bis(styryl)carbazole] and electron‐transporting [dicyano‐p‐quaterphenyl or bis(trifluoromethyl)‐p‐quaterphenyl] fluorophores. The photoluminescence (PL) spectra of the four polymeric films show maximum peaks around 407–413 nm for P1 , P2 and 442–447 nm for P3 , P4 . The PL spectra of P1 ~ P4 are dependent on the composition of the two isolated fluorophores. According to the observation of relative quantum yield in poor solvent (cyclohexane), P2 containing more bulky trifluoromethyl groups in p‐quaterphenyl segments prevented aggregate quenching processes more than P1 . Compared with P1 and P2 with carbazole segments, P3 and P4 with 3,6‐bis(styryl)carbazole segments exhibited less interchain interaction and a low threshold electric field in a single‐layer device. The p‐quaterphenyl and carbazole [or 3,6‐bis(styryl)carbazole] segments were regarded as electron‐transporting and hole‐transporting units, respectively, in the single‐layer light‐emitting diodes (Al/ P1 – P4 /ITO). In the double‐layer device (ITO/MEH‐PPV/ P2 /Al), the maximum luminance was doubled, and the threshold electric fields diminished because P2 functioned as an electron‐transporting and hole‐blocking layer. Furthermore, the voltage‐tunable multicolor emission from orange to green was observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 333–340, 2004  相似文献   

7.
A series of eight poly(p‐phenylene vinylene) (PPV) and poly(p‐phenylene ethynylene) (PPE) ( P1–P8 ) derivatives were tested for their ability to detect the nitroaromatic explosive 2,4,6‐trinitrotoluene (TNT) and its model compound 2,6‐dinitrotoluene (DNT). The polymers P1–P8 represent five structural classes that have not been examined for nitroaromatic sensing. These new motifs include PPE derivatives with a main‐chain m‐terphenyl unit ( P1 ) or oxacyclophane canopy‐like structure ( P2 ) and PPV derivatives with 2,6‐mesitylenephenylene repeats ( P3 and P4 ), 9,9‐dialkyl‐1,4‐fluorenylene repeats ( P5 and P6 ), or m‐phenylene units that periodically disrupt π‐conjugation along the backbone of the polymer ( P7 and P8 ). The time‐dependent photoluminescent response of films to TNT and DNT and the solution‐phase Stern‐Volmer quenching constants for both TNT and DNT were determined. The results are rationalized in terms of side‐chain sterics and π‐system electronics and are discussed relative to known conjugated polymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1487–1492  相似文献   

8.
A donor backbone [poly(para‐divinylphenylamino)]‐acceptor (cyanoacetic acid side group) type conjugated polymer ( P2 ) has been synthesized and used as the active material for dye‐sensitized solar cells. DFT calculation shows that the insertion of vinyl link in the polymer backbone leads to a planar structure in P2 and changes the excited state significantly. Photoelectrochemical cells based on the DSSC format were fabricated using the polymers as sensitizers. The cell constructed using P2 exhibits a considerably high peak IPCE and J‐V response, with an overall power conversion efficiency of 3.67%. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2958–2965  相似文献   

9.
A new aggregation‐induced emission (AIE) active polymer (PS‐TPE) with high tetraphenylethene (TPE) loading density was synthesized. The synthesized polymer showed significant AIE properties, good solubility and high thermal stability. Soft‐lithographic contact printing process by using photoinduced surface relief structures on azo polymer film as masters and duplicated PDMS elastomer as stamps was used to fabricate fluorescent PS‐TPE patterns. Various fluorescent structures with high contrast including surface relief gratings, periodically dotted patterns, and quasi‐crystal structures can be easily fabricated through this approach. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1838–1845  相似文献   

10.
2,6‐bis(4‐Distyrylpyridine) ( 1 ) was synthesized by the condensation of 2,6‐dimethylpyridine with 4‐bromobenzaldehyde. Two new series of soluble random or alternating polyfluorenes ( PF‐Py ) and poly‐p‐phenylenes ( PP‐Py ) with various compositions were prepared by Suzuki coupling utilizing 1 as a comonomer. These polymers showed optical band gaps of 3.00–3.07 eV and photoluminescence (PL) quantum yields in solution of 0.37–0.91 for PF‐Py and 0.29–0.38 for PP‐Py . Polymers PF‐Py emitted blue light with PL maximum at 410–424 nm in solution and 406–428 nm in thin films that was red shifted with increasing distyrylpyridine content. Polymers PP‐Py behaved as blue emitters both in solution and in solid state, with PL maximum at 416–436 nm. The optical properties of these polymers could be tuned by the reversible protonation–deprotonation process of the pyridine ring. The emitted color of the polymers in solution and thin film could be changed continuously between blue and green (PL maximum up to about 520 nm) by exposing the polymers to the acid or base environment. Thin films of PF‐Py displayed excellent color stability with a small red shift of 10 nm but without additional emission band in the long wave region of the spectrum, even after being annealed at high temperature for a long time. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4486–4495, 2005  相似文献   

11.
Poly(3‐hexylthiophene)/single‐walled carbon nanotube (P3HT/SWNT) materials are synthesized using an insitu Grignard metathesis approach. The structural properties and photophysics of the materials are studied using a multitude of techniques, including 1H NMR, FTIR, UV–vis absorption, Raman, photoluminescence (PL), and transient absorption spectroscopies. P3HT/SWNT composites with high P3HT regioregularity (rr > 96%) are observed. Raman spectroscopic data on the solid samples reveals an increase in the dispersion rate parameter with increasing SWNT concentration, thereby indicating close overlap and strong interactions between P3HT and the carbon nanotubes. Changes in the solution‐phase PL quantum yields and excited‐state lifetimes relative to pure P3HT support these conclusions, and indicate that strong interactions persist even after the composites are dispersed in organic solvents. The high regioregularity and enhanced P3HT–SWNT interactions are promising attributes for improving the morphology and efficiency of functional P3HT/SWNT materials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 310–320  相似文献   

12.
Head‐to‐tail regioregular poly(3‐heptanoylthiophene) (PHOT) was synthesized by Ni‐catalyzed polycondensation of the 2,2‐dimethyl‐1,3‐propanediol‐protected Grignard monomer followed by deprotection. Cyclic voltammetric (CV) study demonstrates that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of PHOT are 0.5 eV lower in energy than those of the head‐to‐tail poly(3‐hexylthiophene) (HT‐P3HT). Their optical band gaps are essentially the same. Incomplete photoluminescence (PL) quenching was observed in thin films of the 1:1 blend of PHOT and HT‐P3HT. PHOT displayed a glass transition at ~269 °C and decomposed at ~300 °C according to differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Wide‐angle X‐ray diffraction (WAXD) study showed that PHOT exists in a not highly ordered state in solid films especially in the π‐stacking direction. Only p‐channel activity was observed in field‐effect transistors (FETs) for PHOT. The hole mobility was on the order of 10?4 cm2 V?1 s?1. Photovoltaic devices with an active layer of 1:1 blend of PHOT and PC71BM had a power conversion efficiency (PCE) of ~0.5%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010  相似文献   

13.
Aggregation‐induced emission (AIE) technology has been demonstrated to be a facile approach for in‐situ monitoring atom transfer radical polymerization (ATRP). A series of tertraphenyl ethylene (TPE)‐containing α‐bromo compounds were synthesized and applied as ATRP initiators. The photoluminescent (PL) emission of the polymerization system is proved to be sensitive to the local viscosity owing to the AIE characteristics of TPE. Linear relationships between the resulting molecular weight Mn and PL intensity were observed in several polymerization systems with different monomers, indicating the variability of this technique. Compared to physical blending, the chemical bonding of the TPE group in the chain end has higher sensitivity and accuracy to the polymer segments and the surrounding environment. This work promoted the combination of the AIE technique and controlled living radical polymerization, and introduced such an optical research platform to the ATRP polymerization process.  相似文献   

14.
The formation of ruptured poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐1,4‐phenyl vinylene] (MEH–PPV) thin films coated from undried tetrahydrofuran (THF) solutions was investigated. Because of the incompatibility of water and MEH–PPV, the polymer films coated from THF/water solutions showed a ruptured film structure. In the photoluminescence (PL) spectra of the polymer thin films, the ruptured polymer films showed a redshifted emission in comparison with continuous polymer thin films. According to a comparison of the PL spectra of polymer solutions and films, MEH–PPV in THF showed a coil–cylinder transition during precipitation from solution. Because of the incompatibility of water and MEH–PPV, an increase in the water content could increase the ratio of polymer chains in the cylinder conformation, resulting in a redshifted emission for the films. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 79–84, 2006  相似文献   

15.
A series of boron ketoiminate derivatives that exhibited clear aggregation‐induced emission (AIE) characteristics (in THF: ΦPL≤0.01; in the solid state: ΦPL=0.30–0.76) were prepared by the reactions of 1,3‐enaminoketone derivatives with boron trifluoride–diethyl etherate. The structures and optical properties were investigated by UV‐visible spectroscopy, photoluminescent (PL) spectroscopy, and X‐ray single‐crystal measurements. These results indicate that the AIE characteristics were derived from molecular motions of the boron‐chelating rings with a boron? nitrogen (B? N) bond. Furthermore, the optical properties were controllable by steric hindrance of the substituted groups on the nitrogen atom.  相似文献   

16.
《中国化学会会志》2017,64(10):1190-1196
A series of tetra(biphenyl‐4‐yl)phthalimide (TBPPI ) derivatives with different N‐substituents (n‐butyl, phenyl, p‐methyl phenyl, and p‐acetyl phenyl moieties for compounds 7 – 10 , respectively) were prepared to examine their fluorescent behavior under various conditions. The chemical structure of compound 7 has been successfully confirmed by single crystal X‐ray diffraction analysis. The photoluminescence (PL ) spectra in different ratios of CH 2Cl 2/EtOH mixture solutions revealed that compounds 7 and 8 exhibited both aggregation‐induced emission (AIE ) and aggregation‐caused quenching (ACQ ) behaviors, while compounds 9 and 10 displayed AIE and aggregation‐induced emission enhancement (AIEE ) properties, respectively.  相似文献   

17.
Using a new aromatic 1,2,4‐triazole branching monomer (4.8–13.3 mol %), three hyperbranched polyfluorenes ( P2 – P4 ) were synthesized by the Suzuki coupling reaction to investigate the structural effect on optoelectronic properties. Poly(9,9‐dihexylfluorene) ( P1 ) was also prepared for comparative investigation. Their weight‐average molecular weights and polydispersity indices are in the range of 1.16 × 104 to 5.9 × 104 and 1.49–2.25, respectively. Optical properties, both in solution and film state, were investigated using absorption and photoluminescence (PL) spectra. In film state, the absorption and PL spectra peaked at 377–392 and 424–425 nm, respectively, blue‐shift with increasing triazole concentration. Furthermore, a linear relationship between 1/λmax,abs and 1/(1 ? ntriazole) is correlated (n: molar fraction), indicating a smooth decrease in conjugation length by incorporation of the branch unit. The P4 containing 13.3 mol % triazole reveals stable blue emission even at 150 °C (in air). The HOMO and LUMO levels of P2 – P4 , estimated from cyclic voltammograms, are ?5.69, ?5.73, ?5.78 eV and ?2.63, ?2.64, ?2.63 eV, respectively. The maximal brightness (current efficiency) of the electroluminescent devices (ITO/PEDOT:PSS/ P2 – P4 /Ca/Al) improves from 828 cd/m2 (0.19 cd/A) to 2054 cd/m2 (0.46 cd/A) with increasing triazole concentration. The results suggest that incorporation of aromatic 1,2,4‐triazole branch units is an effective way to improve annealing stability and EL performance of polyfluorenes. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4465–4476, 2007  相似文献   

18.
Two new poly(p‐phenylene vinylene) derivatives OX1‐PPV and OX2‐PPV bearing two 1,3,4‐oxadiazole rings per repeat unit and a fully conjugated backbone with solubilizing dodecyloxy side groups were synthesized and investigated. The amorphous conjugated polymers had glass‐transition temperature values of 60–75 °C and emitted intense blue or greenish‐blue light in solution with photoluminescence (PL) emission maxima at 379–492 nm and PL quantum yields of 0.41–0.52. In the solid state they emitted yellowish‐green light with PL emission maxima at 533–555 nm. Cyclic voltammetry showed that both conjugated polymers had reversible reduction and irreversible oxidation, making them n‐type materials. The electron affinity of OX2‐PPV was estimated as 2.85 eV whereas that of OX1‐PPV was 2.75 eV. Yellow electroluminescence (EL) was achieved from single‐layer light‐emitting diodes of OX2‐PPV with an EL emission maximum at 555 nm and a brightness of 70 cd/m2. Polymer OX2‐PPV, which was functionalized with 2,6‐bis(1,3,4‐oxadiazole‐2‐yl)pyridine, demonstrated sensitivity to various metal ions as a fluorescence‐mode chemosensor. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2112–2123, 2004  相似文献   

19.
A novel conjugated poly[(fluorene‐2,7‐vinylene)‐alt‐(1,4‐phenylenevinylene)] derivative 2 with quaternizable tertiary amino groups was synthesized by Heck coupling of a substituted 2,7‐dibromofluorene and 1,4‐dialkoxy‐2,5‐divinylbenzene. The corresponding quaternary ammonium cationic polyelectrolyte 3 was obtained by the treatment of 2 with bromoethane. Both polymers were soluble in common organic solvents, like tetrahydrofuran, chloroform, and dichloromethane. Polymer 3 showed a limited solubility in alcohols and was insoluble in water. Photophysical and electrochemical properties of the resulting polymers were fully investigated. An intensive green photoluminescence (PL) with maxima at 550 and 545 nm was observed from thin films of 2 and 3 polymers, respectively, red‐shifted compared with the PL emission spectra measured in the solution. The electrochemical band gaps were 2.38–2.45 eV. Single‐layer and double‐layer (with poly[3,4‐(ethylenedioxy)thiophene]/poly (styrenesulfonate) (PEDOT:PSS)) light‐emitting devices (LEDs) with ITO and Al electrodes were prepared and studied. They emitted a green light and their electroluminescence (EL) spectra were similar to those of PL thin films. The external EL efficiency was determined to be 0.43 and 0.32% for ITO/PEDOT:PSS/ 2 /Al and ITO/PEDOT:PSS/ 3 /Al LEDs, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1016–1027, 2007  相似文献   

20.
Three new poly(p‐phenylenevinylene) derivatives—PO, POD, and POP—with oxadiazole and pyridine rings along the main chain were synthesized via Heck coupling. The polymers were amorphous and dissolved readily in common organic solvents. They showed relatively low glass‐transition temperatures (up to 42 °C) and satisfactory thermal stability. Solutions of the polymers emitted blue‐greenish light with photoluminescence (PL) emission maxima around 460 nm and PL quantum yields of 0.28–0.49. Thin films of the polymers displayed PL emission maxima at 461–521 nm, and their tendency to form aggregates was significantly influenced by the chemical structure. Light‐emitting diodes with polymers PO and POP, with an indium tin oxide/poly(ethylenedioxythiophene) (PEDOT)/polymer/Ca configuration, emitted yellow and green light, respectively, and this could be attributed to excimer emission. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3212–3223, 2004  相似文献   

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