Home About us Contact
|
Home About us Contact | ||
|
|
||
Perylene Units (perylene + unit)
Selected AbstractsEnergy- and Charge-Transfer Processes in a Perylene,BODIPY,Pyridine Tripartite ArrayEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 16 2008Mohammed A. H. Alamiry Abstract A novel boron dipyrromethene (BODIPY) dye has been synthesized in which the F atoms, usually bound to the boron center, have been replaced with 1-ethynylperylene units and a 4-pyridine residue is attached at the meso -position. The perylene units function as photon collectors over the wavelength range from 350 to 480 nm. Despite an unfavorable spectral overlap integral, rapid energy transfer takes place from the singlet-excited state of the perylene unit to the adjacent BODIPY residue, which is itself strongly fluorescent. The mean energy-transfer time is 7,±,2 ps at room temperature. The dominant mechanism for the energy-transfer process is Dexter-type electron exchange, with Förster-type dipole,dipole interactions accounting for less than 10,% of the total transfer probability. There are no indications for light-induced electron transfer in this system, although there is evidence for a nonradiative decay channel not normally seen for F -type BODIPY dyes. This new escape route is further exposed by the application of high pressure. The meso -pyridine group is a passive bystander until protons are added to the system. Then, protonation of the pyridine N atom leads to complete extinction of fluorescence from the BODIPY dye and slight recovery of fluorescence from the perylene units. Quenching of BODIPY-based fluorescence is due to charge-transfer to the pyridinium unit whereas the re-appearance of perylene-based emission is caused by a reduction in the Förster overlap integral upon protonation. Other cations, most notably zinc(II) ions, bind to the pyridine N-atom and induce similar effects but the resultant conjugate is weakly fluorescent.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthesis and characterization of high thermally-stable and good soluble PVK-based polymers with perylene moietyJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2008Jianli Hua Abstract Three new poly(N -vinylcarbazole) (PVK)-based copolymers containing N -(n -butyl)- N -ethyl-1,6,7,12-tetra-(4- tert -butyl-phenoxy)-3,4,9,10-perylene tetracarboxylic bisimides were successfully synthesized by partially formylated by the standard Vilsmeier reaction, and the formyl groups of high reactivity are condensed with cyanoacetylated perylene to afford PVK-based polymers. The copolymers containing different percentage of perylene were obtained through the percentage of cyanoacetylated perylene unit being controlled by the initial feed ratio. The structures and properties of three copolymers were characterized and evaluated by FT-IR, NMR, UV,vis, FL spectroscopy, gel permeation chromatography, and thermogravimetric analysis measurements. The polymers were highly soluble in conventional solvents such as toluene, CHCl3, THF, DMF etc., and they were thermally stable up to 442,445°C. Three copolymers have emission spectra with characteristic features of the perylene unit, and fluorescence quantum yields of polymers are higher than that of perylene bisimide, which may be caused by singlet,singlet energy transfer from PVK backbone to perylene in the polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Energy- and Charge-Transfer Processes in a Perylene,BODIPY,Pyridine Tripartite ArrayEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 16 2008Mohammed A. H. Alamiry Abstract A novel boron dipyrromethene (BODIPY) dye has been synthesized in which the F atoms, usually bound to the boron center, have been replaced with 1-ethynylperylene units and a 4-pyridine residue is attached at the meso -position. The perylene units function as photon collectors over the wavelength range from 350 to 480 nm. Despite an unfavorable spectral overlap integral, rapid energy transfer takes place from the singlet-excited state of the perylene unit to the adjacent BODIPY residue, which is itself strongly fluorescent. The mean energy-transfer time is 7,±,2 ps at room temperature. The dominant mechanism for the energy-transfer process is Dexter-type electron exchange, with Förster-type dipole,dipole interactions accounting for less than 10,% of the total transfer probability. There are no indications for light-induced electron transfer in this system, although there is evidence for a nonradiative decay channel not normally seen for F -type BODIPY dyes. This new escape route is further exposed by the application of high pressure. The meso -pyridine group is a passive bystander until protons are added to the system. Then, protonation of the pyridine N atom leads to complete extinction of fluorescence from the BODIPY dye and slight recovery of fluorescence from the perylene units. Quenching of BODIPY-based fluorescence is due to charge-transfer to the pyridinium unit whereas the re-appearance of perylene-based emission is caused by a reduction in the Förster overlap integral upon protonation. Other cations, most notably zinc(II) ions, bind to the pyridine N-atom and induce similar effects but the resultant conjugate is weakly fluorescent.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Macroscopically Aligned Ionic Self-Assembled Perylene-Surfactant Complexes within a Polymer Matrix,ADVANCED FUNCTIONAL MATERIALS, Issue 13 2008Ari Laiho Abstract Ionic self-assembled (ISA) surfactant complexes present a facile concept for self-assembly of various functional materials. However, no general scheme has been shown to allow their overall alignment beyond local polydomain-like order. Here we demonstrate that ionic complexes forming a columnar liquid-crystalline phase in bulk can be aligned within polymer blends upon shearing, taken that the matrix polymers have sufficiently high molecular weight. We use an ISA complex of N,N,-bis(ethylenetrimethylammonium)perylenediimide/bis(2-ethylhexyl) phosphate (Pery-BEHP) blended with different molecular weight polystyrenes (PS). Based on X-ray scattering studies and transmission electron microscopy the pure Pery-BEHP complex was found to form a two-dimensional oblique columnar phase where the perylene units stack within the columns. Blending the complex with PS lead to high aspect ratio Pery-BEHP aggregates with lateral dimension in the mesoscale, having internal columnar liquid-crystalline order similar to the pure Pery-BEHP complex. When the Pery-BEHP/PS blend was subjected to a shear flow field, the alignment of perylenes can be achieved but requires sufficiently high molecular weight of the polystyrene matrix. The concept also suggests a simple route for macroscopically aligned nanocomposites with conjugated columnar liquid-crystalline functional additives. [source] Highly soluble diphenylfluorene-based cardo copolyimides containing perylene units,POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 7-8 2006Shengang Xu Abstract Two series of novel ternary copolyimides containing perylene and fluorene units in the backbone were synthesized by one-step polycondensation of diamine (4,4,-(9H-fluoren-9-ylidene)bisphenylamine, FBPA) with perylene dianhydride (3,4,9,10-perylenetetracarboxylic dianhydride, PTCDA) and a comonomer [4,4,-(hexafluoroisopropylidene) diphthalic anhydride, 6FDA or 3,3,,4,4,-benzophenonetetracarboxylic dianhydride, BDTA]. The polymers were named as PFFx (PTCDA-FBPA-6FDA) and PFBx (PTCDA-FBPA-BTDA), respectively, and their chemical structures were identified by FT-IR spectra and elemental analyses. Perylene contents in the copolyimides were determined through a quantitative UV-vis spectroscopy method, which are in agreement with the values calculated from the added raw materials both for PFFx and PFBx. Gel permeation chromatography (GPC) measurement suggested that the weight average molecular weight (Mw) is in the range 2.1,5.09,×,104 and the molecular weight distribution (MWD) is 1.86,2.72 for PFFx, and those for PFBx are 2.64,4.73,×,104 and 2.44,2.92, respectively. Thermogravimetric analysis (TGA) measurements showed that the copolyimides are very thermally stable with a temperature of 10% weight loss (T10) in the range 546,563°C for PFFx, and 538,548°C for PFBx. The copolyimides also have good solubility in common organic solvents such as chloroform and tetrahydrofuran. These unique properties can be attributed to the existence of the bulky diphenylfluorene moieties in the polymer backbone. All the copolyimides can emit strong fluorescence both in solution and in films, which make them possibly be used as thermostable light-emitting materials for organic light-emitting diodes. Copyright © 2006 John Wiley & Sons, Ltd. [source] | ||||||||||