- Metallated Graphynes as a New Class of Photofunctional 2D Organometallic Nanosheets
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Two-dimensional (2D) nanomaterials are attracting much attention due to their excellent electronic and optical properties. Here, we report the first experimental preparation of two free-standing mercurated graphyne nanosheets via the interface-assisted bottom-up method, which integrates both the advantages of metal center and graphyne. The continuous large-area nanosheets derived from the chemical growth show the layered molecular structural arrangement, controllable thickness and enhanced π-conjugation, which result in their stable and outstanding broadband nonlinear saturable absorption (SA) properties (at both 532 and 1064 nm). The passively Q-switched (PQS) performances of these two nanosheets as the saturable absorbers are comparable to or higher than those of the state-of-the-art 2D nanomaterials (such as graphene, black phosphorus, MoS2, γ-graphyne, etc.). Our results illustrate that the two metallated graphynes could act not only as a new class of 2D carbon-rich materials, but also as inexpensive and easily available optoelectronic materials for device fabrication.
- Huang, Bolong,Li, Jiahua,Sun, Jibin,Sun, Mingzi,Tang, Tianhong,Wang, Zhengping,Wong, Wai-Yeung,Xie, Zheng,Xu, Linli,Zhang, Hongyang,Zhang, Jianqi
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- Self-Assembly of Metallo-Supramolecules under Kinetic or Thermodynamic Control: Characterization of Positional Isomers Using Scanning Tunneling Spectroscopy
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Coordination-driven self-assembly has been extensively employed to construct a variety of discrete structures as a bottom-up strategy. However, mechanistic understanding regarding whether self-assembly is under kinetic or thermodynamic control is less exp
- Wang, Lei,Song, Bo,Li, Yiming,Gong, Lele,Jiang, Xin,Wang, Ming,Lu, Shuai,Lu, Shuai,Hao, Xin-Qi,Xia, Zhenhai,Zhang, Yuan,Zhang, Yuan,Hla, Saw Wai,Li, Xiaopeng
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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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- 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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- Two-photon polarity probes built from octupolar fluorophores: Synthesis, structure-properties relationships, and use in cellular imaging
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A series of octupolar fluorophores built from a triphenylamine (TPA) core connected to electron-withdrawing (EW) peripheral groups through conjugated spacers has been synthesized. Their photoluminescence, solvatochromism, and two-photon absorption (2PA) properties were systematically investigated to derive structure-property relationships. All derivatives exhibit two 2PA bands in the 700-1000 nm region: a first band at low energy correlated with a core-to-periphery intramolecular charge transfer that leads to an intense 1PA in the blue-visible range, and a second more intense band at higher energy due to an efficient coupling of the branches through the TPA core. Increasing the strength of the EW end groups or the length of the conjugated spacers and replacing triple-bond linkers with double bonds induces both enhancement and broadening of the 2PA responses, thereby leading to cross-sections up to 2100 GM at peak and higher than 1000 GM over the whole 700-900 nm range. All derivatives exhibit intense photoluminescence (PL) in low- to medium-polarity environments (with quantum yields in the 0.5-0.9 range) and display a strong positive solvatochromic behavior (with Lippert-Mataga specific shifts ranging from 15 000 to 27 500 cm-1), triple bonds, and phenyl moieties in the conjugated spacers, thereby leading to larger sensitivities than those of double bonds and thienyl moieties. More hydrophilic derivatives were also shown to be biocompatible, to retain their 2PA and PL properties in biological conditions, and finally to be suitable as polarity sensors for multiphoton cell imaging. Copyright
- Le Droumaguet, Celine,Sourdon, Aude,Genin, Emilie,Mongin, Olivier,Blanchard-Desce, Mireille
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- Redox tunable viologen-based porous organic polymers
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The use of an organic donor-acceptor polymer containing a viologen electron acceptor and triarylamine electron donor as a platform in the development of multifunctional materials is presented. The highly robust porous organic polymer (POP) system allows f
- Hua, Carol,Chan, Bun,Rawal, Aditya,Tuna, Floriana,Collison, David,Hook, James M.,D'Alessandro, Deanna M.
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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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- Pyran-annulated perylene diimide derivatives as non-fullerene acceptors for high performance organic solar cells
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There has been growing interest in the effectual strategy of constructing non-fullerene acceptors for organic solar cells that may overcome the defect of traditional fullerene-based acceptors. Herein, two novel push-pull (acceptor-donor-acceptor) type sma
- Li, Gang,Zhang, Yu,Liu, Tao,Wang, Shuaihua,Li, Dandan,Li, Jiewei,Li, Fengting,Yang, Lian-Ming,Luo, Zhenghui,Yang, Chuluo,Yan, He,Hao, Pin,Shang, Qiaoyan,Tang, Bo
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p. 11111 - 11117
(2018/11/03)
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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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- Synthesis, photophysical, electrochemical, and DSSC application of novel donor-acceptor triazole bridged dendrimers with a triphenylamine core and benzoheterazole as a surface unit
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Triazole bridged novel donor-acceptor dendrimers with triphenylamine as the core and benzoheterazole as the surface unit have been synthesized by click chemistry via a convergent approach. All the dendrimers exhibited excellent optical and electrochemical
- Rajavelu, Kannan,Rajakumar, Perumal,Sudip, Mandal,Kothandaraman, Ramanujam
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p. 10246 - 10258
(2016/12/07)
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- Clicked isoreticular metal-organic frameworks and their high performance in the selective capture and separation of large organic molecules
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Three highly porous metal-organic frameworks (MOFs) with a uniform rht-type topological network but hierarchical pores were successfully constructed by the assembly of triazole-containing dendritic hexacarboxylate ligands with ZnII ions. These
- Li, Pei-Zhou,Wang, Xiao-Jun,Tan, Si Yu,Ang, Chung Yen,Chen, Hongzhong,Liu, Jia,Zou, Ruqiang,Zhao, Yanli
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supporting information
p. 12748 - 12752
(2015/10/28)
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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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- Tunable star-shaped triphenylamine fluorophores for fluorescence quenching detection and identification of nitro-aromatic explosives
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Triphenylamine-based fluorophores containing pyrene or corannulene show variable fluorescence quenching sensitivity toward nitro explosives. The most sensitive fluorophore is capable of detecting TNT on the ng cm-2 scale; the array is useful for identifying nitro aromatics.
- Niamnont, Nakorn,Kimpitak, Nattaporn,Wongravee, Kanet,Rashatasakhon, Paitoon,Baldridge, Kim K.,Siegel, Jay S.,Sukwattanasinitt, Mongkol
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supporting information
p. 780 - 782
(2013/02/23)
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- Octupolar derivatives functionalized with superacceptor peripheral groups: Synthesis and evaluation of the electron-withdrawing ability of potent unusual groups
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Novel tripodal derivatives with a triphenylamine core and that bear "superacidifiers" (i.e., fluorinated sulfoximinyl blocks) or novel sulfiliminyl moieties as peripheral groups were synthesized. These new chromophores show strong absorption in the near-U
- Rouxel, Cédric,Le Droumaguet, Céline,Macé, Yohan,Clift, Sophie,Mongin, Olivier,Magnier, Emmanuel,Blanchard-Desce, Mireille
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supporting information
p. 12487 - 12497
(2012/11/07)
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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 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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- Two-photon photosensitized production of singlet oxygen: Sensitizers with phenylene-ethynylene-based chromophores
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(Chemical Equation Presented) Singlet molecular oxygen (a 1Δg) has been produced and optically monitored in time-resolved experiments upon nonlinear two-photon excitation of photosensitizers that contain triple bonds as an integral part of the chromophore. Both experiments and ab initio computations indicate that the photophysical properties of alkyne-containing sensitizers are similar to those in the alkene-containing analogues. Most importantly, however, in comparison to the analogue that contains double bonds, the sensitizer containing alkyne moieties is more stable against singlet-oxygen-mediated photooxygenation reactions. This increased stability can be advantageous, particularly with respect to two-photon singlet oxygen imaging experiments in which data are collected over comparatively long time periods.
- McIlroy, Sean P.,Clo, Emiliano,Nikolajsen, Lars,Frederiksen, Peter K.,Nielsen, Christian B.,Mikkelsen, Kurt V.,Gothelf, Kurt V.,Ogilby, Peter R.
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p. 1134 - 1146
(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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