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A novel and efficient halogen-free composite flame retardant (CFR) consisting of a brucite core and a fine zinc borate [Zn6O(OH)(BO3)3] hierarchical nanostructure shell was designed and synthesized via a facile nanoengineering route. It had been demonstrated that this unique hybrid structure possessed a high BET specific surface area (65 m(2)/g) and could significantly enhance the interfacial interaction when mixing with ethylene-vinyl acetate (EVA). This improved the transfer of stress between CFR particles and EVA matrix and increased the viscosity of EVA/EVA blends, which was beneficial for droplet inhibition and char forming. The mechanical properties and flammability behaviors of the EVA/CFR blends had been compared with the EVA/physical mixture (PM, with the given proportion of brucite and Zn6O(OH)(BO3)3). The mechanical properties of EVA/CFR blends, especially the tensile strength (TS), presented a remarkable increase reaching at least a 20% increment. Meanwhile, with the same 45 wt % of fillers, the EVA/CFR formulation could achieve a limiting oxygen index (LOI) value of 33 (37.5 % higher than that of EVA/PM blends) and UL-94 V-0 rating. Moreover, the heat release rate (HRR), peak heat release rate (PHRR), total heat released (THR), smoke production rate (SPR) and mass loss rate (MLR) were considerably reduced, especially PHRR and SPR for EVA/CFR blends were reduced to 32%. According to this study, the design of fine structure might pave the way for the future development of halogen-free flame retardants combining both enhanced mechanical properties and excellent flame retardant behaviors.

Two new NIR-absorbing BODIPY dyes, each bearing two pyridinium groups, are synthesized and their DNA-binding affinities and DNA photocleavage abilities examined in depth. While one BODIPY dye photocleaves DNA mainly through singlet oxygen, the other photocleaves DNA through both singlet oxygen and hydroxyl radical. To the best of our knowledge, this is the first example of a hydroxyl radical being involved in the photodynamic behavior of BODIPY-type dyes. EPR experiments confirm the ability of these and several related BODIPYs to generate superoxide anion radical and hydroxyl radical. This finding may shed light on the mechanism of BODIPY-based photodynamic therapy (PDT) and open a new avenue for development of more efficient BODIPY-type PDT agents.

By using pyran‐containing donor–acceptor dyes as doping molecules in organic light‐emitting devices (OLEDs), we scrutinize the effects of charge trapping and polarization induced by the guest molecules in the electro‐active host material. Laser dyes 4‐(dicyanomethylene)‐2‐methyl‐6‐[2‐(julolidin‐9‐yl)phenyl]ethenyl]‐4H‐pyran (DCM2) and the novel 4‐(dicyanomethylene)‐2‐methyl‐6‐{2‐[(4‐diphenylamino)phenyl]ethenyl}‐4H‐pyran (DCM‐TPA) are used as model compounds. The emission color of these polar dyes depends strongly on doping concentration, which we have attributed to polarization effects induced by the doping molecules themselves. Their frontier orbital energy levels are situated within the bandgap of the tris(8‐hydroxyquinoline)aluminum (Alq3) host matrix and allow the investigation of either electron trapping or both electron and hole trapping. In the case of DCM‐TPA doping, we were able to show that electron trapping leads to a partial shift of the recombination zone out of the doped Alq3 region. To impede charge‐recombination processes taking place in the undoped host matrix, a charge‐blocking layer efficiently confines the recombination zone inside the doped zone and gives rise to increased luminous efficiency. For a doping concentration of 1 wt.‐% we obtain a maximum luminous efficiency of 10.4 cd A–1. At this doping concentration, the yellow emission spectrum shows excellent color saturation with CIE chromaticity coordinates x, y of 0.49 and 0.50, respectively. In the case of DCM2 the recombination zone is much less affected for the same doping concentrations, which is ascribed to the fact that both electrons and holes are being trapped. The experimental findings are corroborated with a numerical simulation of the doped multilayer devices.

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Three new starburst DCM (4‐(dicyanomethylene)‐2‐methyl‐6‐[4‐(dimethylaminostyryl)‐4H‐pyran]) derivatives, 4,4′,4′′‐tris[2‐(4‐dicyanomethylene‐6‐t‐butyl‐4H‐pyran‐2‐yl)‐ethylene]triphenylamine (TDCM), 4,4′,′′‐tris[2‐(4‐(1′,3′‐indandione)‐6‐t‐butyl‐4H‐pyran‐2‐yl)‐ethylene]triphenylamine (TIN), and 4‐methoxy‐4′,4′′‐bis[2‐(4‐(1′,3′‐indandione)‐6‐t‐butyl‐4H‐pyran‐2‐yl)‐ethylene]triphenylamine (MBIN), have been designed and synthesized for application as red‐light emitters in organic light‐emitting diodes (OLEDs). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) reveal their extremely high glass‐transition temperatures and decomposition temperatures, as well as their low tendency to crystallize. Photoluminescence and electroluminescence measurements show that they exhibit a greatly restricted concentration‐quenching effect compared to DCM1 (4‐(dicyanomethylene)‐2‐methyl‐6‐[p‐(N,N‐dimethylamino)‐styryl]‐4H‐pyran), a simple but typical DCM‐type dye, as a result of their non‐planar, three‐dimensional structures that result from their unique propeller‐like triphenylamine electron‐donating cores. The peripheral electron‐withdrawing moieties also play a key role in the restriction of concentration quenching. That is, TIN and MBIN, bearing 1,3‐indandione acceptors, emit more efficiently than TDCM and DCM1, which have dicyanomethylene as acceptors at a high doping concentration of 10 wt.‐% in poly(9‐vinylcarbazole) (PVK) film, irrespective of whether they are photoexcited or electroexcited, though their fluorescence quantum yields in dilute solutions are much lower than that of DCM1. By way of the co‐doping approach, the electroluminescence device with the configuration indium tin oxide (ITO)/PVK:MBIN(10 wt.‐%):tris(4‐(2‐phenylethynyl)‐phenyl)amine (TPA; 30 wt.‐%) (70 nm)/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline (BCP; 20 nm)/tris(8‐quinolinolato) aluminum (Alq3;15 nm)/LiF (0.3 nm)/Al (150 nm) exhibits a turn‐on voltage of 5.1 V, a maximum luminance of 6971 cd m–2, a maximum efficiency of 6.14 cd A–1 (405 cd m–2), and chromaticity coordinates of (0.66,0.33). The encouraging electroluminescence performance suggests potential applications of the starburst DCM red‐light emitters in OLEDs.

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Ruthenium(II) polypyridyl complexes with long-wavelength absorption and high singlet-oxygen quantum yield exhibit attractive potential in photodynamic therapy. A new heteroleptic Ru(II) polypyridyl complex, [Ru(bpy)(dpb)(dppn)](2+) (bpy=2,2'-bipyridine, dpb=2,3-bis(2-pyridyl)benzoquinoxaline, dppn=4,5,9,16-tetraaza-dibenzo[a,c]naphthacene), is reported, which exhibits a (1)MLCT (MLCT: metal-to-ligand charge transfer) maximum as long as 548 nm and a singlet-oxygen quantum yield as high as 0.43. Steady/transient absorption/emission spectra indicate that the lowest-energy MLCT state localizes on the dpb ligand, whereas the high singlet-oxygen quantum yield results from the relatively long (3)MLCT(Ru-->dpb) lifetime, which in turn is the result of the equilibrium between nearly isoenergetic excited states of (3)MLCT(Ru-->dpb) and (3)pipi*(dppn). The dppn ligand also ensures a high binding affinity of the complex towards DNA. Thus, the combination of dpb and dppn gives the complex promising photodynamic activity, fully demonstrating the modularity and versatility of heteroleptic Ru(II) complexes. In contrast, [Ru(bpy)(2)(dpb)](2+) shows a long-wavelength (1)MLCT maximum (551 nm) but a very low singlet-oxygen quantum yield (0.22), and [Ru(bpy)(2)(dppn)](2+) shows a high singlet-oxygen quantum yield (0.79) but a very short wavelength (1)MLCT maximum (442 nm).