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Dendrons
Terms modified by Dendrons Selected AbstractsLight-Triggered Self-Assembly of a Spiropyran-Functionalized Dendron into Nano-/Micrometer-Sized Particles and Photoresponsive Organogel with Switchable FluorescenceADVANCED FUNCTIONAL MATERIALS, Issue 1 2010Qun Chen Abstract The synthesis, self-assembly, and spectroscopic investigations of spiropyran (SP)-functionalized dendron 1 are reported. Under UV light irradiation, assembly of 1 into nano-/microparticles occurs due to the transformation of the closed form of SP into the open merocyanine (MC) form. The formation of these nano-/microparticles is confirmed by transmission electron microscopy (TEM) and dynamic light scattering (DLS) experiments in addition to the confocal laser scanning microscopy (CLSM) measurements. These nano-/microparticles exhibit relatively strong red emission. It is interesting to note that the direct cooling of the toluene/benzene solution of 1 to 0,°C leads to gel formation. Multivalent ,,, interactions due to the dendron in 1 may be the driving-force for the gelation. The UV light irradiation cannot destroy the gel phase, and in fact, the gel,gel transition is successfully realized. The purple-blue gel exhibits relatively strong red fluorescence; moreover, the fluorescence can be reversibly switched by alternating UV and visible light irradiation. The results clearly indicate that the MC form after aggregation becomes more stable and fluorescent. [source] Super-Stable, High-Quality Fe3O4 Dendron,Nanocrystals Dispersible in Both Organic and Aqueous SolutionsADVANCED MATERIALS, Issue 11 2005M. Kim High-quality Fe3O4 nanocrystals coated with stearate groups are successfully converted to dendron-coated nanocrystals (dendron,nanocrystals). Poly(ethylene glycol) oligomers are used as major terminal groups for the dendron ligands, which afford excellent dispersibility of the dendron,nanocrystals in a broad spectrum of solvents, ranging from dichloromethane to water (see Figure). [source] The Molecular Basis of Self-Assembly of Dendron,Rod,Coils into One-Dimensional NanostructuresCHEMISTRY - A EUROPEAN JOURNAL, Issue 28 2006Eugene R. Zubarev Prof. Abstract We describe here a comprehensive study of solution and solid-state properties of self-assembling triblock molecules composed of a hydrophilic dendron covalently linked to an aromatic rigid rod segment, which is in turn connected to a hydrophobic flexible coil. These dendron,rod,coil (DRC) molecules form well-defined supramolecular structures that possess a ribbonlike morphology as revealed by transmission-electron and atomic-force microscopy. In a large variety of aprotic solvents, the DRC ribbons create stable networks that form gels at concentrations as low as 0.2,% by weight DRC. The gels are thermally irreversible and do not melt at elevated temperatures, indicating high stability as a result of strong noncovalent interactions among DRC molecules. NMR experiments show that the strong interactions leading to aggregation involve mainly the dendron and rodlike blocks, whereas oligoisoprene coil segments remain solvated after gelation. Small-angle X-ray scattering (SAXS) profiles of different DRC molecules demonstrate an excellent correlation between the degree-of-order in the solid-state and the stability of gels. Studies on two series of analogous molecules suggest that self-assembly is very sensitive to subtle structural changes and requires the presence of at least four hydroxyl groups in the dendron, two biphenyl units in the rod, and a coil segment with a size comparable to that of the rodlike block. A detailed analysis of crystal structures of model compounds revealed the formation of stable one-dimensional structures that involve two types of noncovalent interactions, aromatic ,,, stacking and hydrogen bonding. Most importantly, the crystal structure of the rod,dendron compound shows that hydrogen bonding not only drives the formation of head-to-head cyclic structures, but also generates multiple linkages between them along the stacking direction. The cyclic structures are tetrameric in nature and stack into ribbonlike objects. We believe that DRC molecules utilize the same arrangement of hydrogen bonds and stacking of aromatic blocks observed in the crystals, explaining the exceptional stability of the nanostructures in extremely dilute solutions as well the thermal stability of the gels they form. This study provides mechanistic insights on self-assembly of triblock molecules, and unveils general strategies to create well-defined one-dimensional supramolecular objects. [source] Light-Triggered Self-Assembly of a Spiropyran-Functionalized Dendron into Nano-/Micrometer-Sized Particles and Photoresponsive Organogel with Switchable FluorescenceADVANCED FUNCTIONAL MATERIALS, Issue 1 2010Qun Chen Abstract The synthesis, self-assembly, and spectroscopic investigations of spiropyran (SP)-functionalized dendron 1 are reported. Under UV light irradiation, assembly of 1 into nano-/microparticles occurs due to the transformation of the closed form of SP into the open merocyanine (MC) form. The formation of these nano-/microparticles is confirmed by transmission electron microscopy (TEM) and dynamic light scattering (DLS) experiments in addition to the confocal laser scanning microscopy (CLSM) measurements. These nano-/microparticles exhibit relatively strong red emission. It is interesting to note that the direct cooling of the toluene/benzene solution of 1 to 0,°C leads to gel formation. Multivalent ,,, interactions due to the dendron in 1 may be the driving-force for the gelation. The UV light irradiation cannot destroy the gel phase, and in fact, the gel,gel transition is successfully realized. The purple-blue gel exhibits relatively strong red fluorescence; moreover, the fluorescence can be reversibly switched by alternating UV and visible light irradiation. The results clearly indicate that the MC form after aggregation becomes more stable and fluorescent. [source] Control of Charge Transport in Iridium(III) Complex-Cored Carbazole Dendrimers by Generation and Structural ModificationADVANCED FUNCTIONAL MATERIALS, Issue 2 2009Salvatore Gambino Abstract Here, the charge transporting properties of a family of highly phosphorescent iridium(III) complex-cored carbazole dendrimers designed to have improved charge transport by incorporating carbazole units into the dendrons are studied. Firstly, the effect of the dendrimer generation and the role of dendron for materials with one dendron per ligand of the core are considered. It is shown, in contrast to previously reported light-emitting dendrimers, that in this case the carbazolyl-based dendrons have an active role in charge transport. Next, the effect on the charge transport of attaching two dendrons per ligand to the dendrimer core is explored. In this latter case, for the so called "double dendron" material a highly non-dispersive charge transport behavior is observed, together with a time-of-flight mobility of the order of 10,3,cm2 V,1,s,1. Furthermore the lowest energetic disorder parameter (,) ever reported for a solution-processed conjugated organic material is found, ,,< ,20 meV. [source] Mechanically Stretching Folded Nano- ,-b; -stacks Reveals Pico-Newton Attractive ForcesADVANCED MATERIALS, Issue 7 2009Jung Sook Kim Picoforce atomic force microscopy (AFM) and specific DNA hybridization have been used to lock on to synthetic nano-,-stacks, revealing the secrets of thermophilic, albeit weak, ,,, interactions. A cone-shaped dendron created an appropriate lateral spacing to ensure that most times a single stack was confined between the tip and the substrate, eliminating undesired multi-molecular pulling and greatly simplifying data analysis. [source] Super-Stable, High-Quality Fe3O4 Dendron,Nanocrystals Dispersible in Both Organic and Aqueous SolutionsADVANCED MATERIALS, Issue 11 2005M. Kim High-quality Fe3O4 nanocrystals coated with stearate groups are successfully converted to dendron-coated nanocrystals (dendron,nanocrystals). Poly(ethylene glycol) oligomers are used as major terminal groups for the dendron ligands, which afford excellent dispersibility of the dendron,nanocrystals in a broad spectrum of solvents, ranging from dichloromethane to water (see Figure). [source] Dendritic Amplification of Stereoselectivity of a Prolinamide-Catalyzed Direct Aldol ReactionISRAEL JOURNAL OF CHEMISTRY, Issue 1 2009Kazuhiko Mitsui Isomeric "compact" and "expanded" dendrimers functionalized with L -prolinamide catalytic units at the periphery were compared as catalysts to monomer controls in the organocatalytic direct aldol condensation. A positive dendritic effect that amplifies the stereoselectivity of the direct aldol condensation was observed for dendrimers 3 and 4, compared with lower molecular weight catalysts L -prolinani-lide 1 and G1 dendron 2. The difference in the compactness between 3 and 4 appears to have less impact on the stereoselectivity than the preorganized multivalency of the dendritic catalysts. [source] Effect of pH and generation of dendron on single-step synthesis of gold nanoparticles using PEGylated polyamidoamine dendron in aqueous mediumJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 6 2010Atsushi Harada Abstract Three types of PEGylated polyamidoamine (PAMAM) dendrons were synthesized through PEGylation of primary amines at the periphery of second, third, and fourth generation dendrons. Au(III) precursors and the synthesized PEGylated PAMAM dendrons were mixed at various pHs to evaluate the effect of pH on gold nanoparticle (Au NP) synthesis by monitoring the change in surface plasmon resonance. The Au NP synthesis reaction was controlled by pH through the balance between protonated and deprotonated tertiary amines and the reactivity of Au(III) precursors. By using PEGylated PAMAM dendrons with higher generation, the obtained Au NPs had narrow size distribution with small average size because of the limitation of intermolecular space among PEGylated PAMAM dendrons for the growth to Au NP. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1391,1398, 2010 [source] Self-assembled dendron nanotubes: Surface functionalization with maltosyl units and their reversible complexation with Concanavalin AJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 3 2010Mikyoung Yun We described a facile methodology to construct the dendron nanotubes with surface maltosyl unit which can interact specifically with a protein such as Con A. The inclusion of the focal pyrene moiety of the amide dendron into the cavity of 6- O -monomaltosyl-,-CD induced formation of the self-assembled dendron nanotubes which contain maltosyl-CD units on the surface. We investigated not only the complexation of the dendron nanotube with Con A but also dissociation of the complex by using glucose which binds to Con A more strongly than maltose. [source] Dendronized tricyanopyrroline-based chromophores in nonlinear optical active host polymerJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2008Mai Ha Hoang Abstract We synthesized new nonlinear optical (NLO) chromophores containing a 3,5-bis(3,5-bisbenzyloxy-benzyloxy)-benzoate dendron. Tricyanopyrroline (TCP)-based chromophores were designed and prepared by virtue of its strong electron withdrawing property. A soluble polyimide containing 6-({4-[2-(1-allyl-4-cyano-5-dicyanomethylene-2-oxo-2,5-dihydro- 1H -pyrrol-3-yl)-vinyl]-phenyl}-butyl-amino)-hexanoyl group in the side chain was also prepared as an NLO active host polymer. A benzoate dendron was tethered at two different binding positions of the chromophore to yield two different guest molecules. Thin-film composites of these dendronized chromophores dissolved in the NLO active polyimide host were employed to fabricate the electro-optic (EO) samples. The EO properties of new NLO polyimides containing dendronized chromophores were compared with those of the sample with nondendronized plain chromophores. The effect of a bulky dendron on the EO properties was investigated using an in situ reflection technique. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5064,5076, 2008 [source] Photophysical and self-assembly behavior of poly(amidoamine) dendrons with chromophore as scaffold: The effect of dendritic architectureJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2008Bing-Bing Wang Abstract Two series of amphiphiles composed of hydrophilic poly(amidoamine) dendrons (from the first to the third generation) as the shell and hydrophobic aromatic chromophores (3,6-di(maleimidyl)-9-phenyl carbazole and 9-(4,-maleimidyl phenyl)-3-maleimidyl carbazole) as the central scaffold were synthesized. The effect of dendritic architecture on the photophysical properties and the self-assembly behavior of these amphiphiles were studied by UV,vis absorption spectroscopy, fluorescence spectroscopy, and transmission electron microscopy (TEM) measurements. Both the generation of dendritic shell and the location of dendrons at the chromophoric scaffold had great effect on the photophysical properties of these amphiphiles. In addition, different spherical aggregates were formed from these amphiphiles in the aqueous solution at different concentrations. Because of the combined effects of steric hindrance and architecture of dendritic shells, the amphiphiles from G2 dendron with central chromophore self-organized into ordered aggregates more readily than that from G1 and G3. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4584,4593, 2008 [source] Synthesis and self-organization of rod,dendron and dendron,rod,dendron moleculesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2003Sébastien Lecommandoux Abstract We synthesized molecules containing one or two dendritic segments and a rigid-rod-like segment with their structures in the solid state. The molecules with rod,dendron or dendron,rod,dendron architecture had biphenyl ester rigid segments and 3,4,5 tris(n -dodecyloxy)benzoate of first or second generation as their dendritic segments. The variables investigated included the rod segment length as well as dendron generation, and all materials obtained were characterized by optical microscopy, differential scanning calorimetry, and X-ray scattering. Depending on the size of the rod segment and generation number of the dendritic segment, molecules organized into smectic, columnar, or cubic phases, and the symmetries observed were dominated by the anisotropic rod,rod interactions. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3501,3518, 2003 [source] Synthesis of Aromatic Macrocyclic Amphiphiles and their Self-Assembling Behavior in Aqueous SolutionMACROMOLECULAR RAPID COMMUNICATIONS, Issue 11 2010Jung-Keun Kim Abstract A triblock amphiphilic macrocycle consisting of a macrocyclic aromatic segment, a hydrophilic oligo(ethylene oxide) branch, and a hydrophobic alkyl dendron is successfully synthesized and characterized. The resulting cyclic amphiphile is observed to self-assemble into hollow double-layered capsules in aqueous solution, as confirmed by dynamic light scattering and cryogenic transmission electron microscopy investigations. The capsules are able to encapsulate hydrophobic guest molecules through aromatic interactions with high stability. [source] A Click Approach to Chiral-Dendronized Polyfluorene DerivativesMACROMOLECULAR RAPID COMMUNICATIONS, Issue 23 2007Zi-Tong Liu Abstract A new kind of chiral-dendronized binaphthyl-containing polyfluorene derivatives has been synthesized through "click chemistry" efficiently. The resulting copolymers exhibited desirable properties, such as excellent solubility, good thermal stability, and considerably high molecular weights. The photophysical properties of the copolymers were investigated in details, and the results indicated that the combination of chiral binaphthyl unit and bulky dendron could effectively suppress intermolecular packing and aggregation. In addition, the investigation of circular dichroism behavior of these chiral-dendronized copolymers showed a strong Cotton effect at long wavelength (373,379 nm), indicating that the chirality of the binaphthyl units was transferred to the whole polyfluorene backbone. [source] Fluorocarbon End-functionalized Polymers from Poly(arylether) Dendritic InitiatorsMACROMOLECULAR SYMPOSIA, Issue 1 2005A. Pillay Narrainen Abstract Fréchet-type poly(arylether) first and second generation (G1 and G2 respectively) dendrons were prepared from 1-(bromomethyl)-3,5-bis(trifluoromethyl)benzene. The latter and the brominated versions of the two dendrons were successfully employed in the copper mediated living radical polymerization (LRP) of styrene-d8 giving polymers of predictable molecular weights and narrow polydispersities. Contact angle measurements and ion beam analysis were used to explore the adsorption of these materials to the air-polymer surface in blended films with unfunctionalized hydrogenous polystyrene. Although contact angle analysis indicated only modest changes in the hydrophobicity and lipophobicity of the surface, ion beam analysis clearly showed the formation of an excess layer of dendron functionalized polymer at the exposed surface that increased with increasing fluorine content. [source] Design of (Gd-DO3A)n -polydiamidopropanoyl-peptide nucleic acid- D(Cys-Ser-Lys-Cys) magnetic resonance contrast agentsBIOPOLYMERS, Issue 12 2008Nariman V. Amirkhanov Abstract We hypothesized that chelating Gd(III) to 1,4,7-tris(carboxymethylaza)cyclododecane-10-azaacetylamide (DO3A) on peptide nucleic acid (PNA) hybridization probes would provide a magnetic resonance genetic imaging agent capable of hybridization to a specific mRNA. Because of the low sensitivity of Gd(III) as an magnetic resonance imaging (MRI) contrast agent, a single Gd-DO3A complex per PNA hybridization agent could not provide enough contrast for detection of cancer gene mRNAs, even at thousands of mRNA copies per cell. To increase the Gd(III) shift intensity of MRI genetic imaging agents, we extended a novel DO3An -polydiamidopropanoyl (PDAPm) dendrimer, up to n = 16, from the N-terminus of KRAS PNA hybridization agents by solid phase synthesis. A C-terminal D(Cys-Ser-Lys-Cys) cyclized peptide analog of insulin-like growth factor 1 (IGF1) was included to enable receptor-mediated cellular uptake. Molecular dynamic simulation of the (Gd-DO3A-AEEA)16 -PDAP4 -AEEA2 - KRAS PNA-AEEA- D(Cys-Ser-Lys-Cys) genetic imaging nanoparticles in explicit water yielded a pair correlation function similar to that of PAMAM dendrimers, and a predicted structure in which the PDAP dendron did not sequester the PNA. Thermal melting measurements indicated that the size of the PDAP dendron included in the (DO3A-AEEA)n -PDAPm -AEEA2 - KRAS PNA-AEEA- D(Cys-Ser-Lys-Cys) probes (up to 16 Gd(III) cations per PNA) did not depress the melting temperatures (Tm) of the complementary PNA/RNA hybrid duplexes. The Gd(III) dendrimer PNA genetic imaging agents in phantom solutions displayed significantly greater T1 relaxivity per probe (r1 = 30.64 ± 2.68 mM,1 s,1 for n = 2, r1 = 153.84 ± 11.28 mM,1 s,1 for n = 8) than Gd-DTPA (r1 = 10.35 ± 0.37 mM,1 s,1), but less than that of (Gd-DO3A)32 -PAMAM dendrimer (r1 = 771.84 ± 20.48 mM,1 s,1) (P < 0.05). Higher generations of PDAP dendrimers with 32 or more Gd-DO3A residues attached to PNA- D(Cys-Ser-Lys-Cys) genetic imaging agents might provide greater contrast for more sensitive detection. © 2008 Wiley Periodicals, Inc. Biopolymers 89: 1061,1076, 2008. This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source] Self-Assembly and Structural Evolvement of Polyoxometalate-Anchored Dendron ComplexesCHEMISTRY - A EUROPEAN JOURNAL, Issue 27 2010Yang Yang Abstract A cationic dendritic molecule that has alkyl chains has been synthesized and employed to encapsulate anionic polyoxometalates through electrostatic interactions. The prepared surfactant-encapsulated polyoxometalate (SEP) complexes were used as building blocks to fabricate self-assemblies in solution and the solid state. Monodispersion, lamellar, and columnar assemblies of SEP complexes have been characterized in detail. With increasing the number of peripheral cationic dendrons on inorganic clusters, the SEPs undergo changes from globular assemblies to monodispersions in solution and from lamellar assemblies to hexagonal columnar structures in the solid state, depending on the amounts of cationic dendrons in the complexes. The structural evolvement was simulated through consideration of the size and shape of the cationic dendron and polyanionic clusters, and the experimental results are in good agreement with the interpretation of the simulations. The present research demonstrates a new kind of dendritic complex and provides a route for controlling their assembling states by simply alternating the number of cationic dendrons in the complexes. [source] Self-Association of Bis-Dendritic Organogelators: The Effect of Dendritic Architecture on Multivalent Cooperative InteractionsCHEMISTRY - A EUROPEAN JOURNAL, Issue 8 2010Myungeun Seo Dr. Abstract A series of bis-dendritic gelators consisting of a benzamide dendron and an alkyl dendron were synthesized to investigate the dendritic effect on self-assembly. The gelators with a first-generation benzamide (benzamide- G1) dendron or a first-generation alkyl (alkyl- G1) dendron formed stable gels in most aromatic solvents, and their self-assembled fibrillar networks were imaged by electron microscopy. The unbranched molecule (G0 - G0) or the molecule possessing a second-generation benzamide (benzamide- G2) dendron did not form gels. Differential scanning calorimetry, powder X-ray diffraction, and Fourier transform IR studies revealed that introduction of a dendritic branch strongly affected the molecular packing as well as the strength of intermolecular interactions. Furthermore, concentration-dependent diffusion coefficient measurements and the evaluation of association constants by 1H NMR spectroscopy indicated that bis-dendritic gelators with a benzamide- G1 dendron possessed high association constants and formed large aggregates, whereas molecules with a single benzamide formed dimers in chloroform. The formation of self-assembled fibrillar networks was driven by the multivalent and cooperative hydrogen bonding observed in the benzamide- G1 dendrons. ,,, stacking of aromatic groups and van der Waals interactions between alkyl chains also played roles in the self-assembly process, thus indicating that a spatial balance between two dendrons is important. [source] Self-Assembly of Two-Component Gels: Stoichiometric Control and Component SelectionCHEMISTRY - A EUROPEAN JOURNAL, Issue 2 2009Andrew Abstract Two-component systems capable of self-assembling into soft gel-phase materials are of considerable interest due to their tunability and versatility. This paper investigates two-component gels based on a combination of a L -lysine-based dendron and a rigid diamine spacer (1,4-diaminobenzene or 1,4-diaminocyclohexane). The networked gelator was investigated using thermal measurements, circular dichroism, NMR spectroscopy and small angle neutron scattering (SANS) giving insight into the macroscopic properties, nanostructure and molecular-scale organisation. Surprisingly, all of these techniques confirmed that irrespective of the molar ratio of the components employed, the "solid-like" gel network always consisted of a 1:1 mixture of dendron/diamine. Additionally, the gel network was able to tolerate a significant excess of diamine in the "liquid-like" phase before being disrupted. In the light of this observation, we investigated the ability of the gel network structure to evolve from mixtures of different aromatic diamines present in excess. We found that these two-component gels assembled in a component-selective manner, with the dendron preferentially recognising 1,4 - diaminobenzene (>70,%), when similar competitor diamines (1,2- and 1,3-diaminobenzene) are present. Furthermore, NMR relaxation measurements demonstrated that the gel based on 1,4-diaminobenzene was better able to form a selective ternary complex with pyrene than the gel based on 1,4-diaminocyclohexane, indicative of controlled and selective ,,, interactions within a three-component assembly. As such, the results in this paper demonstrate how component selection processes in two-component gel systems can control hierarchical self-assembly. [source] The Molecular Basis of Self-Assembly of Dendron,Rod,Coils into One-Dimensional NanostructuresCHEMISTRY - A EUROPEAN JOURNAL, Issue 28 2006Eugene R. Zubarev Prof. Abstract We describe here a comprehensive study of solution and solid-state properties of self-assembling triblock molecules composed of a hydrophilic dendron covalently linked to an aromatic rigid rod segment, which is in turn connected to a hydrophobic flexible coil. These dendron,rod,coil (DRC) molecules form well-defined supramolecular structures that possess a ribbonlike morphology as revealed by transmission-electron and atomic-force microscopy. In a large variety of aprotic solvents, the DRC ribbons create stable networks that form gels at concentrations as low as 0.2,% by weight DRC. The gels are thermally irreversible and do not melt at elevated temperatures, indicating high stability as a result of strong noncovalent interactions among DRC molecules. NMR experiments show that the strong interactions leading to aggregation involve mainly the dendron and rodlike blocks, whereas oligoisoprene coil segments remain solvated after gelation. Small-angle X-ray scattering (SAXS) profiles of different DRC molecules demonstrate an excellent correlation between the degree-of-order in the solid-state and the stability of gels. Studies on two series of analogous molecules suggest that self-assembly is very sensitive to subtle structural changes and requires the presence of at least four hydroxyl groups in the dendron, two biphenyl units in the rod, and a coil segment with a size comparable to that of the rodlike block. A detailed analysis of crystal structures of model compounds revealed the formation of stable one-dimensional structures that involve two types of noncovalent interactions, aromatic ,,, stacking and hydrogen bonding. Most importantly, the crystal structure of the rod,dendron compound shows that hydrogen bonding not only drives the formation of head-to-head cyclic structures, but also generates multiple linkages between them along the stacking direction. The cyclic structures are tetrameric in nature and stack into ribbonlike objects. We believe that DRC molecules utilize the same arrangement of hydrogen bonds and stacking of aromatic blocks observed in the crystals, explaining the exceptional stability of the nanostructures in extremely dilute solutions as well the thermal stability of the gels they form. This study provides mechanistic insights on self-assembly of triblock molecules, and unveils general strategies to create well-defined one-dimensional supramolecular objects. [source] Synthesis and Binding Properties of Dendritic Oxybathophenanthroline Ligands towards Copper(II)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2005Holger Stephan Abstract Dendritic oxybathophenanthroline ligands (generation 0 to 3) have been synthesized by treatment of 4,7-bis(4,-hydroxyphenyl)-1,10-phenanthroline with the corresponding Fréchet-type dendrons carrying a benzylic bromide function at the focal point. The complexation of copper(II) has been studied by liquid,liquid extraction using the radioisotope 64Cu and time-resolved laser-induced fluorescence spectroscopy (TRLFS) in organic media indicating the formation of 1:3 complexes (Cu:dendritic ligand). Electronic and EPR spectroscopy were used to characterize the copper(II) chromophore, which is shown to have the expected distorted square-planar geometry with two phenanthroline donors coordinated to the copper(II) center. The third dendritic ligand therefore is proposed to be bound by secondary interactions. The stability constants of the 1:3 complexes were found to be in the order of log K , 16 in CHCl3. On the other hand, increasing generation of the dendritic Fréchet-type branches leads to enhanced shielding of the copper ion from the environment. Additional information about this behaviour was obtained by the fluorescence lifetimes, which are much less influenced upon addition of copper(II) salt to solutions of the higher generation ligands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Synthesis of Carrier-Transporting Dendrimers with Perylenebis(dicarboximide)s as a Luminescent CoreEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 4 2006Jianfeng Pan Abstract Well-defined, modular dendrimers enable processing techniques and electronic properties to be tuned independently. Moreover, the dendritic topology can isolate the core chromophore, thus reducing or eliminating strong intermolecular interactions. This paper presents the synthesis of three series of flexible, dendron-functionalized dendrimers as red-light-emitting materials by a convergent approach: (1) carbazole (CZ) or oxadiazole (OXZ) terminated imide-type dendrimers, (2) cascade energy-transferring imide-type dendrimers, and (3) CZ-terminated perylene bay-type dendrimers. They all consist of the luminescent core of perylenebis(dicarboximide)s with specific functional groups of CZ or OXZ at the periphery and are constructed from flexible Fréchet-type poly(aryl ether) dendrons. The chemical structures of the dendrons and dendrimers were determined by standard spectroscopic techniques including 1H and 13C NMR spectroscopy and low/high-resolution mass spectrometry (ESI or MALDI-TOF). The dendrimers are designed on the basis of the following considerations: (1) dendron functionalization to incorporate CZ or OXZ units to realize the carrier-injection adjustment, (2) tuning or improving solubility, functionality, glass-transition temperature (Tg) with well-defined dendrons, and (3) avoiding luminescence quenching with the help of high site-isolation of dendrons to enhance core luminescence. DSC results indicate that the incorporation of Fréchet-type poly(aryl ether) dendrons can improve the amorphous properties and increase Tg. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Control of Charge Transport in Iridium(III) Complex-Cored Carbazole Dendrimers by Generation and Structural ModificationADVANCED FUNCTIONAL MATERIALS, Issue 2 2009Salvatore Gambino Abstract Here, the charge transporting properties of a family of highly phosphorescent iridium(III) complex-cored carbazole dendrimers designed to have improved charge transport by incorporating carbazole units into the dendrons are studied. Firstly, the effect of the dendrimer generation and the role of dendron for materials with one dendron per ligand of the core are considered. It is shown, in contrast to previously reported light-emitting dendrimers, that in this case the carbazolyl-based dendrons have an active role in charge transport. Next, the effect on the charge transport of attaching two dendrons per ligand to the dendrimer core is explored. In this latter case, for the so called "double dendron" material a highly non-dispersive charge transport behavior is observed, together with a time-of-flight mobility of the order of 10,3,cm2 V,1,s,1. Furthermore the lowest energetic disorder parameter (,) ever reported for a solution-processed conjugated organic material is found, ,,< ,20 meV. [source] Dramatic Morphology Control in the Fabrication of Porous Polymer Films,ADVANCED FUNCTIONAL MATERIALS, Issue 22 2008Luke A. Connal Abstract Highly ordered, porous honeycomb films are prepared by the breath-figure (BF) technique using dendron-functionalized star polymers as precursors. By changing the nature of the dendritic end groups, dramatically different porous morphologies can be produced. Three series of star polymers are prepared with both the size of the 2,2-bis(methoxy)propionic acid (bis-MPA)-based dendron end group and the dendron functionality being varied. Star polymers end-functionalized with acetonide-protected dendrons (generations 1 to 4) are initially prepared and the acetonide groups subsequently deprotected to yield hydroxyl-functionalized star polymers. Modification of these hydroxyl groups with pentadecafluorooctanoyl chloride yields a third series of functionalized star polymers. The resulting star polymers have surface groups with very different polarity and by utilizing these star polymers to form honeycomb films by the BF technique, the morphology produced is dramatically different. The star polymers with amphiphilic character afford interconnected porous morphologies with multiple layers of pores. The star polymers with pentadecafluorooctanoyl end groups show highly ordered monolayers of pores with extremely thin walls and represent a new porous morphology that has previously not been reported. The ability to prepare libraries of different dendronized star polymers has given further insights into the BF technique and allows the final porous morphology to be controllably tuned utilizing the functional chain ends and generation number of the dendronized star polymers. [source] Solution-Processible Phosphorescent Blue Dendrimers Based on Biphenyl-Dendrons and Fac -tris(phenyltriazolyl)iridium(III) Cores,ADVANCED FUNCTIONAL MATERIALS, Issue 19 2008Shih-Chun Lo Abstract Solution-processible saturated blue phosphorescence is an important goal for organic light-emitting diodes (OLEDs). Fac -tris(5-aryltriazolyl)iridium(III) complexes can emit blue phosphorescence at room temperature. Mono- and doubly dendronized fac -tris(1-methyl-5-phenyl-3- n -propyl-1H -[1,2,4]triazolyl)iridium(III) 1 and fac -tris{1-methyl-5-(4-fluorophenyl)-3- n -propyl-1H -[1,2,4]triazolyl}iridium(III) 4 with first generation biphenyl-based dendrons were prepared. The dendrimers emitted blue light at room temperature and could be solution processed to form thin films. The doubly dendronized 3 had a film photoluminescence quantum yield of 67% and Commission Internationale de l'Eclairage (CIE) coordinates of (0.17, 0.33). OLEDs comprised of a neat film of dendrimer 3 and an electron transport layer achieved a brightness of 142,cd m,2 at 3.8,V with an external quantum efficiency of 7.9%, and CIE coordinates of (0.18, 0.35). Attachment of the fluorine atom to the emissive core had the effect of moving the luminescence to shorter wavelengths but also quenched the luminescence of the mono- and doubly dendronized dendrimers. [source] Solution-Processible Red Iridium Dendrimers based on Oligocarbazole Host Dendrons: Synthesis, Properties, and their Applications in Organic Light-Emitting Diodes,ADVANCED FUNCTIONAL MATERIALS, Issue 18 2008Junqiao Ding Abstract A series of novel red-emitting iridium dendrimers functionalized with oligocarbazole host dendrons up to the third generation (red-G3) have been synthesized by a convergent method, and their photophysical, electrochemical, and electroluminescent properties have been investigated. In addition to controlling the intermolecular interactions, oligocarbazole-based dendrons could also participate in the electrochemical and charge-transporting process. As a result, highly efficient electrophosphorescent devices can be fabricated by spin-coating from chlorobenzene solution in different device configurations. The maximum external quantum efficiency (EQE) based on the non-doped device configuration increases monotonically with increasing dendron generation. An EQE as high as 6.3% was obtained as for the third generation dendrimer red-G3, which is about 30 times higher than that of the prototype red-G0. Further optimization of the device configuration gave an EQE of 11.8% (13.0,cd A,1, 7.2,lm W,1) at 100,cd m,2 with CIE coordinates of (0.65, 0.35). The state-of-the-art performance indicated the potential of these oligocarbazole-based red iridium dendrimers as solution processible emissive materials for organic light-emitting diode applications. [source] On the Synthesis and Selective Deprotection of Low-Generation Dendrons with Orthogonally Protected Peripheral Amine Groups and a Possible Impact of the Deprotection Conditions on the Stability of Dendronized Polymers' SkeletonsHELVETICA CHIMICA ACTA, Issue 11 2006Rabie Al-Hellani Abstract The synthesis of first- and second-generation dendrons with defined ratios of orthogonally protected amine groups in the periphery ((benzyloxy)carbonyl (Cbz) and (tert -butoxy)carbonyl (Boc) protection) and the degree to which they can be selectively removed are described. The reaction conditions required for these deprotections were applied to methacrylic acid (=,2-methylprop-2-enoic acid) based dendronized polymers carrying the same peripheral protecting groups to investigate whether they have any detrimental interference with the polymer skeleton. Specifically it was explored whether dendrons attached to the backbone could possibly be cleaved off as a whole (de-dendronization). Finally it was investigated how de-dendronizations can be used for quantifying both the dendron-structure perfection and the polymer-backbone configurations. [source] Phosphorus dendrimers and dendrons functionalized with the cage ligand tris(1,2-dimethylhydrazino)diphosphaneHETEROATOM CHEMISTRY, Issue 5 2010Lara-Isabel Rodríguez The synthesis of a new phosphorus dendrimer peripherally functionalized with the cage ligand tris(1,2-dimethylhydrazino) diphosphane is described. In addition, dendrons (dendritic wedges) containing the same cage ligand at the focal point are also reported along with their corresponding ruthenium derivatives, which are thought to be potential catalysts in aqueous media. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:290,297, 2010; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20611 [source] The Development of Light-Emitting Dendrimers for Displays,ADVANCED MATERIALS, Issue 13 2007L. Burn Abstract Dendrimers are now an important class of light-emitting material for use in organic light-emitting diodes (OLEDs). Dendrimers are branched macromolecules that consist of a core, one or more dendrons, and surface groups. The different parts of the macromolecule can be selected to give the desired optoelectronic and processing properties. The first light-emitting dendrimers were fluorescent but more recently highly efficient phosphorescent dendrimers have been developed. OLEDs containing light-emitting dendrimers have been reported to have external quantum efficiencies of up to 16,%. The solubility of the dendrimers opens the way for simple processing and a new class of flat-panel displays. In this Review we show how the structure of the light-emitting dendrimers controls key features such as intermolecular interactions and charge transport, which are important for all OLED materials. The advantages of the dendrimer architecture for phosphorescent emitters and the way the structure can be varied to enhance materials performance and device design are illustrated. [source] | |||||||||||||||||||||||||