- Hyperbranched poly(arylene ethynylene)s with triphenylamine core for polymer light-emitting diodes
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A series of light-emitting hyperbranched poly(arylene ethynylene)s (HB-PAEs) were prepared by the Sonogashira coupling from bisethynyl of carbazole, fluorene, or dialkoxybenzenes (A2 type) and tris(4-iodophenyl)amine (B3 type). For comparison, two linear polymers (L-PAEs) of the HB analogs were also synthesized. The polymers were characterized by Fourier transform infrared, NMR, and GPC. The HB polymers showed excellent solubility in chloroform, THF, and chlorobenzene when compared with their linear analogs. The number-average molecular weight (Mn) of the polymers determined from GPC was found to be in the range of 18,600-34,200. The polymers were thermally stable up to 298-330 °C with only 5% weight loss. The absorption maxima of the polymers were between 354 and 411 nm with optical band gap in the range of 2.5-2.9 eV. The HB polymers were found to be highly fluorescent with photoluminescence quantum yields around 33-42%. The highest occupied molecular orbital energy levels of the polymers calculated from onset oxidation potentials were found to be in the range from -5.83 to -6.20 eV. Electroluminescence (EL) properties of three HB-PAEs and one L-PAE were investigated with device configuration ITO/PEDOT:PSS/Polymer/LiF/Al. The EL maxima of HB-PAEs were found to be in the range of 507-558 nm with turn-on voltages around 7.5-10 V and maximum brightness values of 316-490 cd/m 2. At the same time, linear analog of one HB-PAE was found to show a maximum brightness of 300 cd/m2 at a turn-on voltage of 8.2 V.
- Palai, Akshaya K.,Mishra, Sarada P.,Kumar, Amit,Srivastava, Ritu,Kamalasanan, Modeeparampil N.,Patri, Manoranjan
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- Coherent effects in energy transport in model dendritic structures investigated by ultrafast fluorescence anisotropy spectroscopy
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Measurements of ultrafast fluorescence anisotropy decay in model branched dendritic molecules of different symmetry are reported. These molecules contain the fundamental branching center units of larger dendrimer macromolecules with either three (C3)- or four (Td, tetrahedral)-fold symmetry. The anisotropy for a tetrahedral system is found to decay on a subpicosecond time scale (880 fs). This decay can be qualitatively explained by Foerster-type incoherent energy migration between chromophores. Alternatively, for a nitrogen-centered trimer system, the fluorescence anisotropy decay time (35 fs) is found to be much shorter than that of the tetramers, and the decay cannot be attributed to an incoherent hopping mechanism. In this case, a coherent interchromophore energy transport mechanism should be considered. The mechanism of the ultrafast energy migration process in the branched systems is interpreted by use of a phenomenological quantum mechanical model, which examines the two extreme cases of incoherent and coherent interactions.
- Varnavski, Oleg P.,Ostrowski, Jacek C.,Sukhomlinova, Ludmila,Twieg, Robert J.,Bazan, Guillermo C.,Goodson III, Theodore
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- Star shaped ferrocenyl substituted triphenylamines
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This manuscript reports design and synthesis of star shaped ferrocenyl substituted triphenylamine conjugates (Fc-TPA) 3a-3c by the Pd-catalyzed Sonogshira cross-coupling reaction. Their photophysical and electrochemical properties were investigated, which are a function of the conjugation length. The time dependent density functional (TD-DFT) studies were performed to understand and support the experimental findings. The LUMO could be significantly stabilized by increasing the conjugation. The thermal stability of Fc-TPA 3a-3c can be improved by increasing the conjugation length. The single crystal X-ray structure of Fc-TPA 3a is reported, which show interesting supramolecular interactions leading to the formation of 2D-network.
- Misra, Rajneesh,Maragani, Ramesh,Pathak, Biswarup,Gautam, Prabhat,Mobin, Shaikh M.
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- Silver coordination polymers based on neutral trinitrile ligand: Topology and the role of anion
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One flexible star-shaped bridging molecule tris-(4-cyanophenyl)amine (TCPA) is synthesized from tris-(4-iodophenyl)amine by treatment with CuCN in hexamethylphosphorotriamide (HMPA) as a catalyst in high yield. Anion-template-controlled reactions of TCPA and silver salts give a series of coordination polymers (CPs) with various topological patterns. The complex [Ag(TCPA)(ClO4)]n·nC6H6 (1) forms an undulating 4.82 network, which displays unusual net entanglement. Two 4.82 nets interweave each other to give rise to 2-fold interpenetrating basic layers, which link together via double μ-O perchlorate bridging interactions. The complex [Ag(TCPA)(CF 3SO3)]n·2nC6H6 (2) forms noninterpenetrating (6,3) nets. The solid state structure of [Ag 3(TCPA)(CF3CO2)3] n·nCH2Cl2 (3) also is a (6,3) honeycomb network, differently, including a sphere-type Ag4(CF 3CO2)62- cluster-anion in the host frameworks, which is a rare example of the host cationic network containing a guest cluster-anion. The complexes [Ag(TCPA)(BF4)·0.5H 2O]n·1.5nC6H6 (4), [Ag(TCPA)(ClO4)·0.5H2O]n·nC 7H8·nH2O (5), and [Ag(TCPA)(CF 3SO3)·0.5H2O]n·1. 5nC6H6 (6) exhibit three similar (10,3) networks which form rare net entanglements. Four (10,3) nets interweave to generate a 4-fold interpenetrating assemble, which are closely united together via specific μ2-Owater bridging interactions. The complex [Ag 4(TCPA)2(CF3CO2)3(CF 3SO3)]n·nC6H 6·nCH2Cl2 (7) is a three-dimensional (3D) structure formed via multiple "zigzag" Ag4 chains. In this AgI-TCPA system, the structural diversities and topological differences of these networks result from the flexibilities of the bridging ligand TCPA and the template-effect of anions. The free rotation of three Ph-CN "arms" around the central N moiety results in TCPA adopting different conformation in the self-assembly process by using variational solvent system and/or counterions.
- Ni, Jia,Wei, Kai-Ju,Liu, Yangzhong,Huang, Xiao-Chun,Li, Dan
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- Synthesis and photophysical properties of fluorescent dyes based on triphenylamine, diphenylamine, diphenyl sulfone or triphenyltriazine derivatives containing an acetylene linkage group
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In this study, ten fluorescent dyes were prepared based on three different kinds of central moiety, such as triphenylamine, diphenylsulfone or triphenyltriazine, which was coupled to either carbazole or naphthalimidinyl group via an acetylene linkage group. N-n-Butyl-carbazole, N-phenyl-carbazole or N-n-butyl-naphthalimide was coupled to the individual central moiety of triphenylamine, diphenyl sulfone, 2,4,6-triphenyl-1,3,5-trazine or diphenylamine using a Sonogashira coupling reaction in the final step. All dyes were confirmed their chemical structure by 1H NMR, GC-Mass and elemental analyses. The absorption properties and thermal stabilities of the fluorescent dyes were examined. Density Functional Theory (DFT) and Time-Dependent DFT calculations were carried out, in addition to geometry simulation, by using the Gaussian 09 program. In terms of fluorescence properties in this series, two dyes based on diphenyl sulfonyl and three dyes based on triphenylamine substituted by 1–3 of N-n-butyl-carbazole exhibited a blue emission, whereas three dyes based on triphenylamine substituted by 1–3 of N-n-butyl-naphthalimide were observed by a red emitter which can be attributable to both effects the bathochromic shifts in absorption maxima and larger Stokes shifts. In case of corresponding 2,4,6-triphenyl-1,3,5-trazine central moiety coupled to a carbazole ring, a green fluorescence was emitted. Results revealed that the fluorescence of the dyes is affected by the electron-donating strength of the acetylene linkages involved in the π-conjugation systems of the dyes.
- Ahn, Sung-Ok,Choi, Jae-Hong,Kim, Kyung-Won,Kwon, Su-Hyeon,Lee, Byung-Jun,Lee, Ju-Hong
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- Flame retardant compound and preparation method and application thereof
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The invention provides a flame retardant compound and a preparation method and application thereof, and belongs to the technical field of flame retardants. The flame retardant compound has a structureshown in a formula 1, is a brand new flame retardant variety, is good in compatibility with polymer materials, is an efficient halogen-free intumescent flame retardant, and is excellent in flame retardant property. When the addition amount is 10%, the oxygen index of a PVC material can reach to 29.5%, and the vertical combustion UL94 can reach to V0 level. The preparation method has the advantages of low cost and high yield, and industrial production can be realized. The invention further provides the application of the flame retardant compound in the field of flame retardancy.
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Paragraph 0044-0046; 0051-0053; 0056-0058; 0061-0063
(2019/11/12)
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- Dendritic iridium complex electroluminescent material capable of solution processing and synthetic method thereof
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The invention discloses a dendritic iridium complex electroluminescent material capable of solution processing and a synthetic method thereof. The molecular structure consists of two parts, one part is an iridium complex with room temperature phosphorescence property as a luminescent core, the other part is a racial with high triplet state energy level as a peripheral branch radial, and the two parts are connected through a non-conjugated radical. The molecule is of the structure as shown in the specification, wherein C1 to C3 are ionic dendritic iridium complexes, and C4 to C6 are neutral dendritic iridium complexes of similar structure. R1 and R2 are high triplet state energy level radicals with non-conjugated radical ends. The problems of synthesis, purification, device preparation technology and cost, existing in wet process preparation devices, of iridium complex materials can be solved.
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Paragraph 0084; 0091-0092
(2019/07/04)
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- Synthetic method for tris(4-tetrazolylphenyl)amine
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The invention discloses a synthetic method for tris(4-tetrazolylphenyl)amine, and belongs to the field of material chemistry. The technical scheme is as follows: under alkaline conditions, diphenylamine is reacted with a benzene halide to obtain triphenylamine, the triphenylamine is subjected to a substitution reaction with iodine to form tris(4-iodophenyl)amine, the tris(4-iodophenyl)amine is reacted with CuCN to form tris(4-cyanophenyl)amine, and finally the tris(4-cyanophenyl)amine is reacted with sodium azide to form the tris(4-tetrazolylphenyl)amine. A porous material constructed by a reaction of the prepared tris(4-tetrazolylphenyl)amine and a metal not only has the stability of carboxylic acid porous skeletons, but also realizes the functionalization in the pore channels, and the size of the pore channels can reach a mesoporous size; and the adsorption capacity of specific sulfur-containing small molecules by the tris(4-tetrazolylphenyl)amine further shows the potential application value of the tris(4-tetrazolylphenyl)amine, and the tris(4-tetrazolylphenyl)amine has meaning for development of high-performance petrochemical products.
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- Self-assembly of supramolecular fractals from generation 1 to 5
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In the seeking of molecular expression of fractal geometry, chemists have endeavored in the construction of molecules and supramolecules during the past few years, while only a few examples were reported, especially for the discrete architectures. We herein designed and constructed five generations of supramolecular fractals (G1-G5) based on the coordination-driven self-assembly of terpyridine ligands. All the ligands were synthesized from triphenylamine motif, which played a central role in geometry control. Different approaches based on direct Sonogashira coupling and/or (tpy-Ru(II)- tpy) connectivity were employed to prepare complex Ru(II)-organic building blocks. Fractals G1-G5 were obtained in high yields by precise coordination of organic or Ru(II)-organic building blocks with Zn(II) ions. Characterization of those architectures were accomplished by 1D and 2D NMR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), traveling-wave ion mobility mass spectrometry (TWIM-MS), and transmission electron microscopy (TEM). Furthermore, the two largest fractals also hierarchically self-assemble into ordered supramolecular nanostructures either at solid/liquid interface or in solution on the basis of their well-defined scaffolds.
- Wang, Lei,Liu, Ran,Gu, Jiali,Song, Bo,Wang, Heng,Jiang, Xin,Zhang, Keren,Han, Xin,Hao, Xin-Qi,Bai, Shi,Wang, Ming,Li, Xiaohong,Xu, Bingqian,Li, Xiaopeng
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supporting information
p. 14087 - 14096
(2018/10/20)
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- Multipodal arrangement of push-pull chromophores: a fundamental parameter affecting their electronic and optical properties
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A series of model push-pull molecules with linear, quadrupolar, and tripodal arrangements, a varyingly substituted amino donor, two acceptors, and a partially extended π-system has been prepared. Two peripheral electron acceptors, namely N,N′-dibutylbarbituric acid and dicyanovinyl, were employed. The fundamental properties of 24 push-pull chromophores were investigated by differential scanning calorimetry, electrochemistry, one-photon absorption spectroscopy, photoinduced piezooptics, and were supported by DFT calculations. Thorough structure-property relationships were elucidated, while a significant influence of the structural arrangement/branching on the electronic and optical properties has been revealed. The fundamental optoelectronic properties of push-pull molecules are affected by their arrangement (linear/quadrupolar/tripodal), the peripheral acceptor attached, extension and planarization of the π-system, and also by the type of auxiliary N-substituent.
- Klikar,Kityk,Kulwas,Mikysek,Pytela,Bure?
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supporting information
p. 1459 - 1472
(2017/02/23)
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- Optical properties of triphenylamine decorated with naphthalimide
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A propeller conformed triphenylamine molecule was decorated with naphthalimide. The two fluorophores were bonded with alkynyl bridge unit, which conjugates the two fragments. The resulting compound was fully characterized. Several solvents were used to investigate its absorption and emission behavior with the solvent polarity variation from weak to strong. The quantum yield increased with the increasing of solvent polarity. It is also highly emissive in film and in a solid with significant emission shift toward longer wavelength, reaching to 544 and 593?nm, respectively. The underlying signal mechanism was interpreted by the HOMO/LUMO potentials based on TDDFT calculations.
- Li, Xiaochuan,Li, Anqi,Jiang, Wenjuan,Son, Young-A
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- Hollow and microporous triphenylamine networks post-modified with TCNE for enhanced organocathode performance
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Hollow microporous triphenylamine networks (H-MTPN) were post-modified with tetracyanoethylene (TCNE) to generate tetracyanobutadiene moieties in H-MTPN-TCNE. The H-MTPN-TCNE showed the improved electrochemical performance of cathode materials for lithium ion batteries, compared to the original H-MTPN.
- Choi, Jaewon,Kim, Eui Soon,Ko, Ju Hong,Lee, Sang Moon,Kim, Hae Jin,Ko, Yoon-Joo,Son, Seung Uk
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supporting information
p. 8778 - 8781
(2017/08/10)
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- Efficient and straightforward click synthesis of structurally related dendritic triazoles
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A simple, rapid and efficient copper-catalyzed 1,3-dipolar cycloaddition reaction is described for the synthesis of a novel family of twelve triazolic dendrimers structurally related. The products were the result of the click reaction of three cores and four different azides in tetrahydrofuran applying a homogeneous copper catalysis. The reaction intermediates and products were obtained in very good to excellent yields using straightforward and simple work-up procedures. This new family of compounds contain electroactive moieties such as carbazole and triphenylamine which may turn them into excellent candidates for the development of optoelectronic organic materials.
- Mangione,Spanevello,Anzardi
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p. 47681 - 47688
(2017/10/23)
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- Solvent and branching effect on the two-photon absorption properties of push-pull triphenylamine derivatives
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The photophysical and two-photon absorption (2PA) properties of two tri-podal molecules and of their quadrupolar and dipolar counterparts are reported for a series of solvents with varying polarity. The molecules possess a tri-phenylamine electron donating group and mono-cyano acceptors while olefinic and acetylenic π-linkers have been used. Branching led to an increase of the molar extinction coefficient and to a slight bathochromic shift of the absorption spectra while the fluorescence quantum yields decrease but they are maintained to relatively high values. Solvatochromic measurements in the tri-podal molecules revealed an emitting state with a polar nature. The 2PA cross sections in general increase upon branching but the observed behaviour strongly depends on the type of solvent. The highest 2PA cross sections are obtained in solvents of medium polarity and values as high as 1420 GM are reported.
- Cvejn,Michail,Seintis,Klikar,Pytela,Mikysek,Almonasy,Ludwig,Giannetas,Fakis,Bure?
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p. 12819 - 12828
(2016/02/12)
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- Evidence for Interfacial Halogen Bonding
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A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2(e-)/Dye-X+, with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F Dye-Cl Dye-Br Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species.
- Swords, Wesley B.,Simon, Sarah J.C.,Parlane, Fraser G.L.,Dean, Rebecca K.,Kellett, Cameron W.,Hu, Ke,Meyer, Gerald J.,Berlinguette, Curtis P.
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p. 5956 - 5960
(2016/05/19)
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- Tuning optical and electronic properties of poly(4,4'-triphenylamine vinylene)s by post-modification reactions
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New triphenylamine-based polyarylenevinylenes with pendant phenylethynyl- and 3-pyridylethynyl substituents were synthesized by Stille polycondensation of trans-1,2-bis(tributylstannyl)ethene with two new ethynyl substituted triphenylamine monomers, i.e., N,N-bis(4-iodophenyl)-4'-(phenylethynyl) phenylamine and N,N-bis(4-iodophenyl)-4'-(3-pyridylethynyl) phenylamine. The polymers were characterized by spectral methods and cyclic voltammetry and their properties were compared with those of the unsubstituted poly(4,4'-triphenylamine vinylene). Chemical post-modifications of the polymers by tetracyanoethylene addition to the triple bond, and quaternization of pyridyl group with accent on the fine-tuning of the optical and electrochemical properties were also studied. Density functional theory calculations provide a reliable interpretation of the observed spectra and electrochemical data.
- Grigoras, Mircea,Catargiu, Ana Maria,Ivan, Teofilia,Vacareanu, Loredana,Minaev, Boris,Stromylo, Evgeniy
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p. 227 - 238
(2015/02/19)
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- Modulation of (non)linear optical properties in tripodal molecules by variation of the peripheral cyano acceptor moieties and the π-spacer
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A series of twelve tripodal push-pull molecules with a central triphenylamine donor and peripheral cyano substituted acceptors has been prepared. These molecules possess systematically altered π-linkers as well as cyano acceptors. Based on the experimental properties measured by differential scanning calorimetry, electrochemistry, one and two photon absorption/emission spectroscopy, supported by the DFT calculations, thorough structure-property relationships were elucidated.
- Cvejn,Michail,Polyzos,Almonasy,Pytela,Klikar,Mikysek,Giannetas,Fakis,Bure
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supporting information
p. 7345 - 7355
(2015/08/11)
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- Synthesis and optical properties of multibranched and C3 symmetrical oligomers with benzene or triphenylamine core and diazines as peripheral groups
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We report therein the synthesis and photophysical properties of a new series of two- and tribranched compounds built up from benzene or triphenylamine as central core and electron-withdrawing diazine rings as peripheral group. The arms allowing connection between these two parts are constituted by an ethynylene linker. All these compounds are fluorescent and are of particular interest with generally good quantum yields and good Stokes shifts. Some of them have been tested for two-photon absorption (TPA) properties and had revealed interesting performances.
- Martin, Flavia-Adina,Baudequin, Christine,Fiol-Petit, Catherine,Darabantu, Mircea,Ramondenc, Yvan,Plé, Nelly
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p. 2546 - 2555
(2014/04/03)
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- A 3D luminescent metal-organic framework constructed from Cu 4I4 cubane clusters and triangular imidazole ligand
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The solvothermal reaction between cuprous iodide and the rigid triangular imidazole ligand in mixed N,N'-dimethylacetamide (DMA)-acetonitrile solvent leads to the isolation of the 3D metal-organic framework [(Cu4I 4)3(TIPA)4]·7DMA (1) [TIPA = tri(4-imidazolylphenyl) amine], which was characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Topologically, the structure of 1 is an unprecedented 3,3,4,4-connected net with a point symbol of {4.8.10}2{4.82}2{4 2.82.102}2{84.12 2}. Compound 1 exhibits orange-red photoluminescence with an emission maximum at 622 nm at room temperature. Copyright
- Liu, Shan-Shan,Yuan, Shuai,Hu, Tuo-Ping,Sun, Di
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p. 2030 - 2034
(2014/11/08)
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- Two-photon lithography in visible and NIR ranges using multibranched-based sensitizers for efficient acid generation
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We investigated methodically the one- and two-photon absorption properties of a series of multibranched triphenylamine-based chromophores incorporating 4-(methylthio)styryl fragments as external substituents. Some relevant structure-property relationships relative to these highly fluorescent compounds have been derived based on emission anisotropy measurements, quantum chemical calculations and the use of the exciton coupling theory. Even though branching effects lead to a cooperative enhancement of the two-photon absorption (2PA), all compounds exhibit relatively low-to-moderate 2PA cross-sections (δ ≤ 100 GM) in the NIR region. However, the 'so-called' one-photon resonance enhancement effect leads to a remarkable increase of δ by more than one order of magnitude in the visible range. This strong 2PA ability has been associated with an efficient photosensitization of iodonium salt to elaborate a new bicomponent photoacid generator, which is readily two-photon activable at 532 nm. In the visible range, the strong enhancement of the efficiency of the two-photon induced polymerization is clearly demonstrated as compared with that observed in the NIR region. This journal is the Partner Organisations 2014.
- Jin, Ming,Xie, Jianchao,Malval, Jean-Pierre,Spangenberg, Arnaud,Soppera, Olivier,Versace, Davy-Louis,Leclerc, Tiffanie,Pan, Haiyan,Wan, Decheng,Pu, Hongting,Baldeck, Patrice,Poizat, Olivier,Knopf, Stephan
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p. 7201 - 7215
(2014/12/10)
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- Tetracyanoethylene substituted triphenylamine analogues
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A set of tetracyanoethylene (TCNE) substituted triphenylamine analogues (4-6) exhibiting strong intramolecular charge transfer (ICT) were designed and synthesized by the [2+2] cycloaddition-retroelectrocyclization reaction of 3 (tris-(4-phenylethynyl-phenyl)-amine) with TCNE. The reaction was found to be temperature dependent. The blue shift in the π → π? transition and intramolecular charge transfer (ICT) in amines 4-6 were found to be directly proportional to the number of TCNE units. The computational study shows good agreement with the experimental results and reveals that as the number of TCNE units in amine increases, HOMO-LUMO gap increases.
- Misra, Rajneesh,Maragani, Ramesh,Gautam, Prabhat,Mobin, Shaikh M.
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p. 7102 - 7105
(2015/01/08)
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- Blue aggregation-induced emission luminogens: High external quantum efficiencies up to 3.99% in LED device, and restriction of the conjugation length through rational molecular design
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Great efforts have been devoted to seek novel approaches for constructing blue fl uorescent materials, which is one of the most important prerequisites for the commercialization of OLEDs. In recent years, various outstanding luminogens with aggregation-induced emission characteristic exhibit promising applications as emitters, but blue AIE fl uorophores with excellent EL performance are still very scarce. Here, fi ve hole-dominated blue AIE molecules are demonstrated by adopting construction approaches of changing linkage modes and increasing intramolecular torsion together, with the aim to restrict conjugation lengths without sacrifi cing good EL data. Device results show that the novel synthesized materials could be applied as bifunctional materials, namely blue light-emitting and hole-transporting materials, with comparable EL efficiencies, and the ηC,max and ηext,max are up to 8.03 cd A-1 and 3.99% respectively, which is among the best EL performance for blue AIE luminogens.
- Huang, Jing,Sun, Ning,Yang, Jie,Tang, Runli,Li, Qianqian,Ma, Dongge,Li, Zhen
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p. 7645 - 7654
(2015/02/19)
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- Synthesis and characterization of 2D-D-π-A-type organic dyes bearing bis(3,6-di-tert-butylcarbazol-9-ylphenyl)aniline as donor moiety for dye-sensitized solar cells
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A series of novel 2D-D-π-A-type organic dyes, namely CCTTnA (n = 1-3), bearing bis(3,6-di-tert-butylcarbazol-9-ylphenyl)aniline as an electron-donor moiety (2D-D), oligothiophene segments with a number of thiophene units from one to three units as π-conjugated spacers (π), and cyanoacrylic acid as the electron acceptor (A) were synthesized and characterized as dye sensitizers for dye-sensitized solar cells (DSSCs). These compounds exhibit high thermal and electrochemical stability. Detailed investigations of these dyes reveal that both peripheral carbazole donors (2D) have beneficial influence on the red-shifted absorption spectrum of the dye in solution and dye adsorbed on TiO2 film, and the broadening of the incident monochromatic photon-to-current conversion efficiency (IPCE) spectra of the DSSCs, leading to enhanced energy conversion efficiency (η). Among these dyes, CCTT3A shows the best photovoltaic performance, and a maximal incident monochromatic photon-to-current conversion efficiency (IPCE) value of 80 %, a short-circuit photocurrent density (Jsc) of 9.98 mA cm-2, open-circuit voltage (Voc) of 0.70 V, and fill factor (FF) of 0.67, corresponding to an overall conversion efficiency η of 4.6 % were achieved. This work suggests that organic dyes based on this type of donor moiety or donor molecular architecture are promising candidates for improved performance DSSCs. New 2D-D-π-A-type organic dyes incorporating bis(3,6-di-tert-butylcarbazol-9- ylphenyl)aniline as an electron-donor moiety show great potential as sensitizers for dye-sensitized solar cells. Copyright
- Khanasa, Tanika,Jantasing, Nittaya,Morada, Somphob,Leesakul, Nararak,Tarsang, Ruangchai,Namuangruk, Supawadee,Kaewin, Tinnagon,Jungsuttiwong, Siriporn,Sudyoadsuk, Taweesak,Promarak, Vinich
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p. 2608 - 2620
(2013/06/27)
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- Synthesis, characterization and properties of novel star-shaped π-conjugated oligomers with triphenylamine core
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Four new star-shaped π-conjugated oligomers (TPA-CZ3, TPA-TPA3, TPA-PTZ3 and TPA-BT3) with triphenylamine as a core and different electron-donating ability groups, carbazole, triphenylamine, phenothiazine and bithiophene, as peripheral units have been designed and synthesized via the Heck reaction. These oligomers show good solubility in common organic solvents. Their photophysical, electrochemical, electronic structure and charge transfer properties between these star-shaped π-conjugated oligomers and N,N′-bis(1-ethylpropyl)-3, 4:9,10-perylene bis(tetracarboxyl diimide) (EP-PDI) have been investigated by UV-vis absorption spectra, photoluminescence (PL) spectra, cyclic voltammetry (CV) measurement, theoretical calculations and fluorescence quenching. The results show that the absorptions and fluorescences of TPA-CZ3, TPA-TPA3 and TPA-PTZ3 are red shifted with the electron-donating ability of the peripheral unit increasing from carbazole to triphenylamine and phenothiazine. In addition, although the bithiophene group has a weaker electron-donating ability than carbazole, triphenylamine and phenothiazine, the absorption and fluorescence of TPA-BT3 have a red shift than those of TPA-CZ3, TPA-TPA3 and TPA-PTZ3 because TPA-BT3 has a longer conjugation length than TPA-CZ3, TPA-TPA3 and TPA-PTZ3. The triphenylamine core and the peripheral units can constitute a large conjugated structure. The fluorescence quenching properties indicate that efficient charge transfer can happen between the star-shaped oligomers and EP-PDI. The core of these new star-shaped oligomers is electron-donating group, triphenylamine. The peripheral units are four hole-transporting chromophores with different electron-donating ability. The photophysical properties of these oligomers can be tuned through changing the electron-donating ability and conjugation length of the peripheral units.
- Liu, Leijing,Guo, Qing,Li, Jiyang,Yao, Bin,Tian, Wenjing
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p. 456 - 464
(2013/08/25)
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- Tuning two-photon absorption cross-sections for triphenylamine derivatives
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A methylene bridge link connecting the ortho-positions within the triphenylamine scaffold increases the molecular planarity significantly. The one-photon spectroscopies of bridged triphenylamine molecules show considerable extended conjugation relative to their triphenylamine counterparts, leading to enhanced two-photon absorption (TPA) cross-sections. Various substituents at the scaffold have been prepared and studied. Using a femtosecond laser source Z-scan method, the TPA cross-sections were characterized. The maximum magnitude of the TPA cross-section is ～4800 GM, which is four times that of its triphenylamine counterpart. The Royal Society of Chemistry.
- Fang, Zhen,Webster, Richard D.,Samoc, Marek,Lai, Yee-Hing
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p. 17914 - 17917
(2013/10/01)
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- Synthesis and properties of azulene-substituted donor-acceptor chromophores connected by arylamine cores
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1-Ethynylazulenes connected by several arylamine cores reacted with tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) in a formal [2+2] cycloaddition-cycloreversion reaction to afford the corresponding tetracyanobutadiene (TCBD) and dicyanoquinodimethane (DCNQ) chromophores, respectively, in excellent yields. The intramolecular charge-transfer (ICT) characters between the donor (azulene and arylamine cores) and acceptor (TCBD and DCNQ units) moieties were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the new TCBD and DCNQ derivatives was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions. 1-Ethynylazulenes connected by several types of arylamine cores reacted with TCNE and TCNQ in formal [2+2] cycloadditions to afford corresponding tetracyanobutadiene and dicyanoquinodimethane chromophores, respectively. Cyclic voltammetry of the chromophores revealed their multistep reduction properties; significant color changes were also visible during electrochemical reduction. Copyright
- Shoji, Taku,Shimomura, Erika,Maruyama, Mitsuhisa,Maruyama, Akifumi,Ito, Shunji,Okujima, Tetsuo,Toyota, Kozo,Morita, Noboru
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p. 7785 - 7799
(2013/12/04)
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- Synthesis and photophysical properties of tetraphenylethylene-based conjugated dendrimers with triphenylamine core
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Two new conjugated dendrimers bearing a tetraphenylethylene moiety as dendrons and triphenylamine as a core have been synthesized through a convergent synthetic strategy using threefold Heck/threefold Sonogashira coupling reaction. These dendrimers showed excellent solubility in common organic solvents and emit light in the blue and violet regions.
- Jana, Debabrata,Ghorai, Binay K.
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body text
p. 196 - 199
(2012/02/17)
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- Copper(i) coordination polymers of 2,2′-dipyridylamine derivatives: Syntheses, structures, and luminescence
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Reactions of CuX (X = Br-, I- or CN-) with various types of 2,2′-dipyridylamine (dpa) derivatives have been performed via a hydrothermal-solvothermal method and the products have been structurally characterized by X-ray crystallography. Four ligands with different coordination motifs were employed in the reactions, including angular N,N,N′,N′-tetra(2-pyridyl)-2,6-pyridinediamine (tppda); linear N,N,N′,N′-tetra(2-pyridyl)-1,4-phenylenediamine (tppa) and N,N,N′,N′-tetra(2-pyridyl)biphenyl-4,4′-diamine (tpbpa); and star-shaped tris-[4-(2,2′-dipyridylamino)-phenyl]amine (tdpa), which yielded eight copper(i) complexes exhibiting different stoichiometries of Cu-dpa and variable coordination modes of dpa. The compound [Cu2(tppda) (μ-I)2]n (1) forms a one dimensional (1D) coordination polymer exclusively through double μ2-I bridges, which arranges to two dimensional (2D) metal-organic frameworks (MOFs) via the face-to-face π...π stacking interactions from pyridyl rings. The compound [Cu 6(tppa)(μ3-Br)6]n (2) forms a 2D network linked through multiple μ3-Br bridges. The compound [Cu2(tppa)(μ-CN)2]n (3) is also a 2D MOF containing 1D (CuCN)n chains. The compounds [Cu(tpbpa)Br]n (4) and [Cu4(tpbpa)2(μ-I)4]n (5) display two different 1D assemblies: a zig-zag chain for 4 and a linear structure for 5. The compound [Cu4(tpbpa)(μ-CN)4] n (6) shows a pseudo-4,82 topological net, while the compound [Cu8(tpbpa)(μ-CN)8]n· 2nH2O (7) exhibits a three-dimensional (3D) framework containing a ...PM... double helical structure, although both of them contain (CuCN)n chains. The compound [Cu2(tdpa)(μ-I) 2]n (8) is a zig-zag chain based on the star-shaped molecule tpda, in which one of three dpa-arms is free of coordination to metal ions. All complexes exhibit luminescence in the solid state.
- Ni, Jia,Wei, Kai-Ju,Min, Yuanzeng,Chen, Yaowen,Zhan, Shunze,Li, Dan,Liu, Yangzhong
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scheme or table
p. 5280 - 5293
(2012/05/20)
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- Star-shaped tripodal chemosensors for the detection of aliphatic amines
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In this work, three new tripodal triphenylamine dyes are presented that are capable of reversibly binding amines and diamines to form hemiaminals through a covalent bond. The dyes were synthesized by the Heck reaction and possess stilbene units with one, two, or three trifluoroacetyl groups as receptor moieties. Their interaction with amines and diamines led to changes in their absorption and emission properties, which were detected by UV/Vis and fluorescence spectroscopy. The influence of the number of trifluoroacetyl receptor moieties on the selectivity and sensitivity of the dyes was studied. Enhanced sensitivity and selectivity for diaminoalkanes was found for the dye we have labeled Tripod-1, with three chemically reactive trifluoroacetyl groups, related to only one or two trifluoroacetyl groups in the dye molecule. Copyright
- Koersten, Susanne,Mohr, Gerhard J.
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experimental part
p. 969 - 975
(2011/03/20)
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- Synthesis and characterization of highly soluble two-photon-absorbing chromophores with multi-branched and dendritic architectures
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A set of novel multi-polar compounds composed of four fluorene-based derivatives with systematic alteration of the molecular structure was synthesized and their nonlinear optical properties in the femtosecond and nanosecond time domain were examined. Preliminary experimental results show that the two-photon activities of the model compounds are connected to structural parameters, such as the number of peripheral electron-donating groups and/or the size of the π-domain in a dye molecule. It is also found that these model chromophores possess large nonlinear attenuation under the irradiation of laser pulses working at nanosecond regimes, indicating that these compounds may have strong two-photon-assisted excited-state absorption within the studied spectral region. Effective optical-power-limiting behaviors of the dendritic fluorophores were also demonstrated to show that such dye molecules can be potential materials for use as broadband and rapid-responsive optical limiters, especially against laser lights with longer pulses.
- Lin, Tzu-Chau,Lin, Wei-Lun,Wang, Chih-Ming,Fu, Chih-Wei
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experimental part
p. 912 - 921
(2011/04/17)
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- Benzothiazoles with tunable electron-withdrawing strength and reverse polarity: A route to triphenylamine-based chromophores with enhanced two-photon absorption
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A series of dipolar and octupolar triphenylamine-derived dyes containing a benzothiazole positioned in the matched or mismatched fashion have been designed and synthesized via palladium-catalyzed Sonogashira cross-coupling reactions. Linear and nonlinear optical properties of the designed molecules were tuned by an additional electron-withdrawing group (EWG) and by changing the relative positions of the donor and acceptor substituents on the heterocyclic ring. This allowed us to examine the effect of positional isomerism and extend the structure-property relationships useful in the engineering of novel heteroaromatic-based systems with enhanced two-photon absorption (TPA). The TPA cross-sections (δTPA) in the target compounds dramatically increased with the branching of the triphenylamine core and with the strength of the auxiliary acceptor. In addition, a change from the commonly used polarity in push-pull benzothiazoles to a reverse one has been revealed as a particularly useful strategy (regioisomeric control) for enhancing TPA cross-sections and shifting the absorption and emission maxima to longer wavelengths. The maximum TPA cross-sections of the star-shaped three-branched triphenylamines are ～500-2300 GM in the near-infrared region (740-810 nm); thereby the molecular weight normalized δTPA/MW values of the best performing dyes within the series (2.0-2.4 GM?g-1?mol) are comparable to those of the most efficient TPA chromophores reported to date. The large TPA cross-sections combined with high emission quantum yields and large Stokes shifts make these compounds excellent candidates for various TPA applications, including two-photon fluorescence microscopy.
- Hrobarik, Peter,Hrobarikova, Veronika,Sigmundova, Ivica,Zahradnik, Pavol,Fakis, Mihalis,Polyzos, Ioannis,Persephonis, Peter
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experimental part
p. 8726 - 8736
(2012/01/05)
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- Synthesis, two-photon absorption, and optical power limiting of new linear and hyperbranched conjugated polyynes based on bithiazole and triphenylamine
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Two new linear and hyperbranched conjugated polymers P1 and P2 have been synthesized by Sonogashira coupling reaction, in which the main chain consists of bithiazole moieties as electron acceptors and triphenylamino groups as donors. The conjugated polymers were characterized by TGA, UV-vis absorption, fluorescence emission, electrochemical cyclic voltammetry, and two-photon absorption measurements. They exhibited excellent solubility in organic solvents and high thermal stability (5% of weight loss at 299 °C). The two-photon absorption cross sections (σ) measured by the open aperture Z-scan technique using 140 femtosecond (fs) pulse were determined to be 1014 and 552 GM per repeating unit for P1 and P2, respectively. This result shows that the σ of linear conjugated P1 is higher than that of hyperbranched P2, indicating that the linear polymer offers better intramolecular charge transfer ability. In THF, P1 and P2 exhibit intense frequency up-converted fluorescence under the excitation of 140 fs pulses at 800 nm with the peaks located at 580 and 548 nm, respectively. Meanwhile, the optical limiting behaviors for the polymers were studied by using a focused 800 nm laser beam of 140 fs duration. It was found that these polymers also exhibit good optical-limiting properties and make them potential candidates for optical limiters in the photonic fields.
- Jiang, Yihua,Wang, Yaochuan,Yang, Jiabao,Hua, Jianli,Wang, Bing,Qian, Shiqiong,Tian, He
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experimental part
p. 1830 - 1839
(2012/03/10)
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- An unprecedented 2D → 3D metal-organic polyrotaxane framework constructed from cadmium and a flexible star-like ligand
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An unprecedented 2D → 3D metal-organic polyrotaxane framework, based on a new star-like tri(4-imidazolylphenyl)amine ligand, has been synthesized and characterized, which represents the first example of 2D → 3D polyrotaxane entangled in a parallel fashion.
- Wu, Hua,Liu, Hai-Yan,Liu, Ying-Ying,Yang, Jin,Liu, Bo,Ma, Jian-Fang
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supporting information; scheme or table
p. 1818 - 1820
(2011/03/22)
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- Two unprecedented 3D metal-organic polyrotaxane frameworks based on a new flexible tri(imidazole) ligand
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Two Cd(ii)-containing coordination polymers based on a new tri(4-imidazolylphenyl)amine (Tipa) ligand and carboxylates, namely, [Cd(Tipa)(L1)]·2H2O (1) and [Cd3(Tipa) 2(L2)2Cl2]·4H2O (2), where H2L1 = 5-OH-1,3-benzenedicarboxylic acid and H2L2 = 1,4-benzendicarboxylic acid, have been synthesized by varying the carboxylates under hydrothermal conditions. In 1, adjacent Cd(ii) centers are linked by L1 anions to generate Cd-carboxylate chains, which are further extended by Tipa ligands to form a puckered double sheet. The most peculiar feature of 1 is the entangled fashion between the [Cd2(Tipa)2] loop and the L1 ligand rod. Every [Cd2(Tipa)2] loop of each layer is threaded by one L1 ligand rod of an adjacent layer. In this entangled mode, the 2D → 3D polyrotaxane framework was obtained, which represents an unusual 2D → 3D metal-organic polyrotaxane framework entangled in a highly rare parallel fashion. In 2, two identical 3D self-penetrating frameworks interpenetrate each other in a 2-fold mode. If we regard each Cd 2(Tipa)2 window as a loop and each L2 ligand as a single rod, undoubtedly, the structure of 2 also can be described as a 3D metal-organic polyrotaxane framework. As far as we know, compound 2 is the first example of a 2-fold interpenetrating 3D framework with polyrotaxane features. The luminescent properties for the two compounds were also investigated.
- Wu, Hua,Liu, Hai-Yan,Liu, Bo,Yang, Jin,Liu, Ying-Ying,Ma, Jian-Fang,Liu, Yun-Yu,Bai, Hong-Ye
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scheme or table
p. 3402 - 3407
(2012/03/22)
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- Synthesis and mesomorphic behaviour of new discotic liquid crystalline compounds containing triphenylamine as a core moiety via Sonogashira coupling
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Design and synthesis of cholesterol based disk-like liquid crystalline compounds using triphenylamine as a core moiety have been achieved by Pd-catalyzed cross-coupling reaction. The newly synthesized compounds exhibit a cholesteric phase with fingerprint texture as well as oily texture. In the low temperature region, there is a signature of smectic B with characteristic dendritic and mosaic textures. The mesogenic properties were characterized by polarizing microscopy, differential scanning calorimetry and HRXRD studies.
- Majumdar,Mondal, Shovan,De, Nirupam,Sinha, Randhir Kumar,Pal, Nilasish,Roy
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scheme or table
p. 521 - 524
(2010/09/20)
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- Bridged Organosilane and Production Method Thereof
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Provided is a bridged organosilane, which has a large complex organic group, and which is useful in the synthesis of a mesoporous silica and a light-emitting material, and a production method of the bridged organosilane. The bridged organosilane is expressed by the following general formula (1): [in the formula (1), q represents an integer in a range from 2 to 4, X1— represents a substituent selected from the group consisting of substituents expressed by the following general formulae (2) to (5): (in the formulae (2) to (5), R1 represents alkyl group having 1 to 5 carbon atoms, R2 represents an allyl group, and n represents an integer in a range from 0 to 3, and m represents an integer in a range from 0 to 6), and A1 represents an organic group expressed by, for example, the following general formula (6): (in the formula (6), Y1 represents a substituent expressed by, for example, O═C)].
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Page/Page column 43-44
(2009/04/24)
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- IBX-I2 redox couple for facile generation of IOH and I +: Expedient protocol for iodohydroxylation of olefins and iodination of aromatics
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(Chemical Equation Presented) IBX is readily reduced to IBAin the presence of molecular iodine in DMSO to generate hypoiodous acid (IOH), which reacts with a variety of olefins as well as R, β-unsaturated ketones leading to their respective iodohydrins with anti stereochemistry. The same redox chemistry in acetonitrile containing TFA produces iodonium ions for facile iodination of a variety of aromatic compounds in respectable isolated yields.
- Moorthy, Jarugu Narasimha,Senapati, Kalyan,Kumar, Sarvesh
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supporting information; experimental part
p. 6287 - 6290
(2009/12/08)
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- CROSSLINKABLE HOLE-TRANSPORTING MATERIALS FOR ORGANIC LIGHT-EMITTING DEVICES
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Crosslinkable compounds useful for making hole-transporting materials for organic light-emitting devices, hole-transporting layers made from the crosslinkable compounds, and light-emitting devices that include the hole-transporting layers.
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- A polyanionic dendritic fluorophore for selective detection of Hg 2+ in triton X-100 aqueous media
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A serles of water-soluble fluorescent dendritic compounds composed of phenylene-ethynylene repeating units and anionic carboxylate or catlonlc ammonium peripheral groups were synthesized. The first generation fluorescent dendrlmer containing nine phenylene-ethynylene units and six carboxylate peripheral groups exhibited a highly selective fluorescence quenching by Hg 2+ Ions. The Stern-Volmer constant (K8v) was 33,700 M -1 In aqueous media In the presence of Triton X-100 surfactant.
- Niamnont, Nakorn,Siripornnoppakhun, Warathip,Rashatasakhon, Paltoon,Sukwattanasinitt, Mongkol
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supporting information; experimental part
p. 2768 - 2771
(2009/11/30)
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- A new disc-shaped mesogenic compound with olefinic linkage derived from triphenylamine: synthesis, mesogenic behavior and fluorescence properties
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A new disc-like triphenylamine containing mesogenic compound has been synthesized by the implementation of the Heck and ring-closing metathesis-based reactions in good yield. The designed and synthesized compound showed rectangular columnar mesophase and this is the first report of liquid crystalline phase of the triphenylamine-based compound with an olefinic linkage. The disc-shaped compound exhibited excellent fluorescence properties.
- Majumdar, Krishna C.,Chattopadhyay, Buddhadeb,Shyam, Pranab Kumar,Pal, Nilasish
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scheme or table
p. 6901 - 6905
(2010/04/30)
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- Organosilane compound and organosilica obtained therefrom
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Provided is an organosilane compound expressed by any one of the following general formulae (1) to (7): (wherein: Ar represents a phenylene group or the like; R1 represents a hydrogen atom or the like; R2 to R8 each represent a methyl group or the like; n represents an integer in a range from 0 to 2; m represents an integer of 1 or 2; L represents a single bond or the like; X represents a hydrogen atom or the like; and Y represents a hydrogen atom or the like).
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Page/Page column 17
(2008/12/07)
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- Investigation of two-photon absorption properties in branched alkene and alkyne chromophores
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Novel alkene and alkyne branched structures have been synthesized, and their two-photon absorption (2PA) properties are reported. This series of alkene and alkyne trimer systems tests the mechanistic approach for enhancing the 2PA process which is usually dictated by the π-bridging, delocalization length, and corresponding charge transfer on the 2PA cross sections. The results suggest that alkene branched systems have higher 2PA cross sections. While steady-state absorption and emission measurements were not successful in predicting the observed trend of 2PA cross sections, time-resolved measurements have explained the trends observed. It was found that, upon photoexcitation, there is an ultrafast charge localization to an intramolecular charge-transfer (ICT) state, followed by the presence of a solvent and conformationally relaxed ICT state in these branched systems.
- Bhaskar, Ajit,Ramakrishna, Guda,Lu, Zhikuan,Twieg, Robert,Hales, Joel M.,Hagan, David J.,Van Stryland, Eric,Goodson III, Theodore
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p. 11840 - 11849
(2007/10/03)
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- Enhanced Two-Photon Absorption with Novel Octupolar Propeller-Shaped Fluorophores Derived from Triphenylamine
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(Equation presented) Novel octupolar fluorophores derived from the symmetrical functionalization of a triphenylamine core with strong acceptor peripheral groups via phenylene-ethynylene linkers have been synthesized and shown to exhibit high fluorescence quantum yields, very large TPA cross-sections in the red-NIR region, and suitable photostability.
- Porres, Laurent,Mongin, Olivier,Katan, Claudine,Charlot, Marina,Pons, Thomas,Mertz, Jerome,Blanchard-Desce, Mireille
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- Polyaromatic amines. Part 2. Synthesis of 4,4′,4″-tris(N-aryl-N-phenylamino)triphenylamine, N,N-bis[4-(N-aryl-N-phenylamino)-phenyl]tolylamine and N,N,N′,N′-tetraaryl-o-phenylenediamine derivatives
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The title compounds were synthesised and characterised as part of a study into new aromatic amines for charge transporting materials. Proton and carbon spectral data for compounds 1-6 were obtained in C6D6 as a consequence of their facile oxidation in CDCl3. Each compound was characterised by cyclic voltammetry. An estimate of the intramolecular charge mobility was deduced from the difference between the first and second oxidation potentials.
- Plater,Jackson
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p. 2548 - 2552
(2007/10/03)
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- Starburst Molecules for Amorphous Molecular Materials. 4,4',4''-Tris(N,N-diphenylamino)triphenylamine and 4,4',4''-Tristriphenylamine
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A novel class of starburst molecules for making amorphous glassy organic materials, 4,4',4''-tris(N,N-diphenylamino)triphenylamine (TDATA) and 4,4',4''-tristriphenylamine (MTDATA), are synthesized and characterized.Their electrochemical and electronic properties as well as unique solid-state morphology are described.
- Shirota, Yasuhiko,Kobata, Tomokazu,Noma, Naoki
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p. 1145 - 1148
(2007/10/02)
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