RESUMEN
The preparation and photophysical properties of heteroleptic iridium(III) complexes containing a dianionic C,C,C,C-tetradentate ligand and a cyclometalated phenylpyridine group are described. Complex [Ir(µ-OMe)(COD)]2 (1, COD = 1,5-cyclooctadiene) reacts with 1,1-diphenyl-3,3-butylenediimidazolium iodide ([PhIm(CH2)4ImPh]I2), in the presence NaOtBu, to give [Ir(µ-I){κ4- C, C, C, C-[C6H4Im(CH2)4ImC6H4]}]2 (2), which leads to {[Ir{κ4- C, C, C, C-[C6H4Im(CH2)4ImC6H4]}]2(µ-OH)(µ-OMe)} (3) by treatment first with silver trifluoromethanesulfonate (AgOTf) in acetone-dichloromethane and subsequently with KOH in methanol. The reaction of 2 with AgOTf and acetonitrile affords the bis(solvento) complex [Ir{κ4- C, C, C, C-[C6H4Im(CH2)4ImC6H4]}(CH3CN)2]OTf (4). The latter promotes the pyridyl-supported heterolytic ortho-CH bond activation of the phenyl group of 2-phenylpyridine, 2-(2,4-difluorophenyl)pyridine, 2-( p-tolyl)pyridine, and 5-methyl-2-phenylpyridine to yield Ir{κ4- C, C, C, C-[C6H4Im(CH2)4ImC6H4]}{κ2- C, N-[Ar-py]} (Ar-py = C6H4-py (5), C6H2F2-py (6), C6H3Me-py (7), C6H4-Mepy (8)) using (piperidinomethyl)polystyrene as an external base. Complexes 5-8 are blue-green emitters, which display short lifetimes (0.6-4.8 µs) and quantum yields close to unity in both doped poly(methyl methacrylate) films at 5 wt % and in 2-methyltetrahydrofuran at room temperature.
RESUMEN
A new class of phosphorescent tris-heteroleptic iridium(III) complexes has been discovered. The addition of PhMeImAgI (PhMeIm = 1-phenyl-3-methylimidazolylidene) to the dimer [Ir(µ-Cl)(COD)]2 (1; COD = 1,5-cyclooctadiene) affords IrCl(COD)(PhMeIm) (2), which reacts with 1-phenylisoquinoline, 2-phenylpyridine, and 2-(2,4-difluorophenyl)pyridine to give the respective dimers [Ir(µ-Cl){κ2- C, C-(C6H4-ImMe)}{κ2- C, N-(C6H4-isoqui)}]2 (3), [Ir(µ-Cl){κ2- C, C-(C6H4-ImMe)}{κ2- C, N-(C6H4-py)}]2 (4), and [Ir(µ-Cl){κ2- C, C-(C6H4-ImMe)}{κ2- C, N-(C6F2H2-py)}]2 (5), as a result of the N-heterocyclic carbene (NHC)- and N-heterocycle-supported o-CH bond activation of the aryl substituents and the hydrogenation of a C-C double bond of the coordinated diene. In solution, these dimers exist as a mixture of isomers a (Im trans to N) and b (Im trans to Cl), which lie in a dynamic equilibrium. The treatment of 3-5 with Kacac (acac = acetylacetonate) yields isomers a (Im trans to N) and b (Im trans to O) of Ir{κ2- C, C-(C6H4-ImMe)}{κ2- C, N-(C6H4-isoqui)}(κ2- O, O-acac) (6a and 6b), Ir{κ2- C, C-(C6H4-ImMe)}{κ2- C, N-(C6H4-py)}(κ2- O, O-acac) (7a and 7b), and Ir{κ2- C, C-(C6H4-ImMe)}{κ2- C, N-(C6F2H4-py)}(κ2- O, O-acac) (8a and 8b), which were separated by column chromatography. The treatment of 6a with HX in acetone-water produces the protonation of the acac ligand and the formation of the bis(aquo) complex [Ir{κ2- C, C-(C6H4-ImMe)}{κ2- C, N-(C6H4-isoqui)}(H2O)2]X [X = BF4 (9a[BF4]), OTf (9a[OTf])]. The salt 9a[BF4] reacts with 2-(2-pinacolborylphenyl)-5-methylpyridine in the presence of 40 equiv of K3PO4 to afford Ir{κ2- C, C-(C6H4-ImMe)}{κ2- C, N-(C6H4-isoqui)}{κ2- C, N-(C6H4-Mepy)} (10a). Complexes 6a, 6b, 7a, 7b, 8a, 8b, and 10a are phosphorescent emitters (λem = 465-655 nm), which display short lifetimes in the range of 0.2-5.6 µs. They show high quantum yields both in doped poly(methyl methacrylate) films (0.34-0.87) and in 2-methyltetrahydrofuran at room temperature (0.40-0.93). From the point of view of their applicability to the fabrication of organic-light-emitting-diode devices, a notable improvement with regard to those containing two cyclometalated C,N ligands is achieved. The introduction of the cyclometalated aryl-NHC group allows one to reach a brightness of 1000 cd/m2 at a lower voltage and appears to give rise to higher luminous efficacy and power efficacy.
RESUMEN
Molecular phosphorescent heteroleptic bis-tridentate iridium(III) emitters have been prepared via η1 -arene intermediates. In the presence of 4.0â mol of AgOTf, the complex [(IrCl{κ3 -N,C,N-(pyC6 HMe2 py)})(µ-Cl)]2 (1; pyC6 H2 Me2 py=1,3-di(2-pyridyl)-4,6-dimethylbenzene) reacted with 9-(6-phenylpyridin-2-yl)-9H-carbazole (PhpyCzH) and 2-phenoxy-6-phenylpyridine (PhpyOPh) to give [Ir{κ3 -N,C,N-(pyC6 HMe2 py)}{κ3 -C,N,C'-(C6 H4 pyCzH)}]OTf (2) and [Ir{κ3 -N,C,N-(pyC6 HMe2 py)}{κ3 -C,N,C'-(C6 H4 pyOPh)}]OTf (3). The X-ray diffraction structures of 2 and 3 reveal that the carbazolyl and phenoxy substituents of the C,N,C' ligand coordinate to the metal center to form an η1 -arene π bond. Treatment of 2 and 3 with KOtBu led to the deprotonation of the coordinated carbon atom of the η1 -arene group to afford the molecular phosphorescent [5t+4t'] heteroleptic iridium(III) complexes [Ir{κ3 -N,C,N-(pyC6 HMe2 py)}{κ3 -C,N,C'-(C6 H4 pyCz)}] (4) and [Ir{κ3 -N,C,N-(pyC6 HMe2 py)}{κ3 -C,N,C'-(C6 H4 pyOC6 H4 )}] (5). These complexes are green emitters that display short lifetimes and high quantum yields of 0.73 (4) and 0.87 (5) in the solid state.
RESUMEN
A MHC6 complex of a platinum group metal with a capped octahedral arrangement of donor atoms around the metal center has been characterized. This osmium compound OsH{κ(2) -C,C-(PhBIm-C6 H4 )}3 , which reacts with HBF4 to afford the 14 e(-) species [Os{κ(2) -C,C-(PhBIm-C6 H4 )}(Ph2 BIm)2 ]BF4 stabilized by two agostic interactions, has been obtained by reaction of OsH6 (PiPr3 )2 with N,N'-diphenylbenzimidazolium chloride ([Ph2 BImH]Cl) in the presence of NEt3 . Its formation takes place through the C,C,C-pincer compound OsH2 {κ(3) -C,C,C-(C6 H4 -BIm-C6 H4 )}(PiPr3 )2 , the dihydrogen derivative OsCl{κ(2) -C,C-(PhBIm-C6 H4 )}(η(2) -H2 )(PiPr3 )2 , and the five-coordinate osmium(II) species OsCl{κ(2) -C,C-(PhBIm-C6 H4 )}(PiPr3 )2 .
RESUMEN
Residues of hexachlorohexanes isomers (HCHs) and dichlorodiphenyltrichloroethane and metabolites (DDTs) in the soils and sediments of Dayanghan Wetland in Wuhu, China were investigated. The concentrations of ΣHCH in soils and sediments averaged 1.35 and 3.77 µg/kg with the predominance of ß-HCH and δ-HCH, respectively. The concentrations of ΣDDT in soils and sediments averaged of 7.80 and 2.80 µg/kg, respectively, with the dominance of o, p'-DDT. The concentrations of HCHs in the soils and sediments and DDTs in the sediments were categorized as no pollution, but the level of DDTs in the soils was classified as low pollution.
Asunto(s)
DDT/análisis , Hexanos/análisis , Hidrocarburos Clorados/análisis , Residuos de Plaguicidas/análisis , Contaminantes del Suelo/análisis , Urbanización , Humedales , ChinaRESUMEN
Controlled neo-endothelialization is critical to the patency of vascular grafts. Expanded polyethylene terephthalate (PET) vascular grafts were grafted with polyethylene glycol (PEG), irradiated with ultraviolet light, and subsequently coated with silk fibroin (SF) and EDC in a dip-coating process. Endothelial cells were cultivated on the coated samples for 1, 3, 5, and 7 days, and characterized by fluorescence microscopy and scanning electron microscopy (SEM). The quantitative analyse of CCK-8 method was used to assess ECs proliferation. The results reveal the correlation between grafting components and cell adhesion. We demonstrated that PET with SF grafting facilitated cell adhesion and spreading. Following 7 days of cell culture in vitro, PET-PEG6000-SF (PEG molecular weight 6,000) displayed spreading of cells over a significantly larger area. Rapid endothelialization on a modified PET surface resulted in large tissue pack that can be observed by SEM.
Asunto(s)
Fibroínas , Prótesis Vascular , Adhesión Celular , Células EndotelialesRESUMEN
[structure: see text] Thiophene dendrons and dendrimers were designed and synthesized using a convergent approach. Metal-mediated coupling reactions were used in the synthesis. A rational approach allowed the formation of alphaalpha, betabeta, and alphabeta linkages between the dendrons and thiophene units.
RESUMEN
Various free radical surface initiated polymerization (SIP) conditions were investigated on clay nanoparticles coated with monocationic 2,2'-azobisisobutyronitrile (AIBN) type free radical initiators. Interesting differences in the mechanism of polymer nanocomposite product formation and the role of nanoparticle surface bound AIBN initiators were observed on three types of poly(methyl methacrylate) (PMMA) polymerization conditions: bulk, suspension, and solution. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) measurements confirmed the attachment of the initiator on the clay particles without decomposition of the azo group. XRD and transmission electron microscopy (TEM) showed that a well-dispersed structure was accomplished only by bulk and solution SIP. The suspension SIP product consisted of a partially exfoliated structure as shown by XRD and clay particle aggregate formation as shown by TEM. In general, the molecular weights (MWs) of the surface bound polymers were found to be lower than those of the free polymer. Using the same clay loading and initiator concentrations, we observed that relatively higher MW polymers were obtained from suspension and bulk polymerizations in contrast to solution method. However, the most interesting observation is that the surface bound polymers (on all three conditions) showed much narrower polydispersity compared to that of a typical AIBN type free radical polymerization.
RESUMEN
We report the synthesis and characterization of dendritic thiophene derivatives with their unique supramolecular assembly into 2-D crystals, nanowires, and nanoparticle aggregates. The structure and size of the dendrons and dendrimers have been confirmed with various techniques, such as NMR, SEC, and MALDI-TOF-MS. The mass values were consistent with the mass observed by MALDI-TOF-MS, whereas SEC measurements also gave useful information on the hydrodynamic volume of the individual dendrimers. The interesting electrooptical properties were highlighted by very broad absorption spectra and narrower fluorescence consistent with their electrochemical behavior. The self-organization of the dendrimers on the solid substrate is dependent on the nature of the substrate, preparation methods, and the molecule-molecule and molecule-substrate interactions. Thus, 14T-1 and 30T both formed globular aggregates on mica surface, while 14T-1 also formed nanowires on graphite surface. On the other hand, the larger 30T was observed to form 2-D crystalline structures. By varying the alkyl chain length attached to 14T-1, we were also able to obtain 2-D crystals on graphite. This showed that the different symmetry of packing for 30T and 14T-1 is also dependent on several factors, such as the molecular shape, size, and the presence of noncovalent intermolecular interactions. The results demonstrated the unique ability of thiophene dendrimers to form nanostructures on surfaces.