1732-13-4Relevant academic research and scientific papers
Synthesis, Photophysical, and Electrochemical Properties of Pyrenes Substituted with Donors or Acceptors at the 4- or 4,9-Positions
Ji, Lei,Krummenacher, Ivo,Friedrich, Alexandra,Lorbach, Andreas,Haehnel, Martin,Edkins, Katharina,Braunschweig, Holger,Marder, Todd B.
, p. 3599 - 3606 (2018)
We report herein an efficient and direct functionalization of the 4,9-positions of pyrene by Ir-catalyzed borylation. Three pinacol boronates (-Bpin), including 4-(Bpin)-2,7-di(tert-butyl)pyrene (5), 4,9-bis(Bpin)-2,7-di(tert-butyl)pyrene (6), and 4,10-bis(Bpin)-2,7-di(tert-butyl)pyrene (7), were synthesized. The structures of 6 and 7 have been confirmed by single-crystal X-ray diffraction. To demonstrate the utility of these compounds, donor (NPh2)-substituted compounds 4-diphenylamino-2,7-di(tert-butyl)pyrene (1) and 4,9-bis(diphenylamino)-2,7-di(tert-butyl)pyrene (2) have been synthesized on a gram scale. Acceptor (BMes2)-substituted compounds 4,9-bis(BMes2)pyrene (3) and 4,9-bis(BMes2)-1,2,3,6,7,8-hexahydropyrene (4) were synthesized for comparison. The photophysical and electrochemical properties of compounds 1-4 have been studied both experimentally and theoretically. The S0 → S1 transitions of the 4- or 4,9-disubstituted pyrenes, 1-3, are allowed, with moderate fluorescence quantum yields and radiative decay rates. The photophysical and electrochemical properties of 1-3 were compared with the 2,6-naphthalenylene-cored compound 4 as well as the previously reported 2,7- and 1,6- pyrenylene-cored compounds.
Synthesis and Electroluminescence of Novel Pyrene-Fused Chromophores
Lee, Jaehyun,Park, Jongwook
, p. 3960 - 3963 (2015)
Using 4,9-dibromopyrene as a key intermediate, two new fused-core compounds, TP-PFF and TP-PFC-TP, were synthesized. These compounds not only exhibited excellent thermal stability but also yielded superior electroluminescence (EL) devices with a lower turn-on voltage, over 50% greater efficiency, and over 3 times longer lifetime than did a similar compound lacking a fused core. This new core-forming method can be applied in various applications with many different core groups.
A novel 4-hydroxypyrene-based “off–on” fluorescent probe with large Stokes shift for detecting cysteine and its application in living cells
Han, Xiang'en,He, Menglu,Li, Jingyang,Ni, Zhonghai,Sun, Wenhao,Tang, Xinxue,Zhang, Ran,Zhao, Yun
, (2019)
This paper reports a novel fluorescent probe 4-acrylatepyrene (PYAC) based on 4-hydroxypyrene, which can effectively detect cysteine (Cys). The probe PYAC uses acrylate moiety as a recognition site and has relatively high selectivity and sensitivity for Cys with the detection limit of 0.062 μM. After treatment with Cys, PYAC exhibits “off–on” switching property and large Stokes shift (171 nm). Due to nucleophilic addition and specific intramolecular cyclization, it exhibits higher selectivity for Cys than other amino acids and common ions, including homocysteine (Hcy) and glutathione (GSH) with similar structures to Cys. The recognition mechanism has been characterized by high-performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (1H NMR). Anti-interference test and pH influence test display it is suitable for detecting Cys in living cells. Finally, the probe PYAC has been successfully applied to cell imaging with negligible cytotoxicity.
Comparison Study of the Site-Effect on Regioisomeric Pyridyl-Pyrene Conjugates: Synthesis, Structures, and Photophysical Properties
Lu, Qing,Kole, Goutam Kumar,Friedrich, Alexandra,Müller-Buschbaum, Klaus,Liu, Zhiqiang,Yu, Xiaoqiang,Marder, Todd B.
, p. 4256 - 4266 (2020)
To investigate the "site effect" of pyridyl substituents on a pyrene core, four regioisomeric monopyridyl-pyrene (1-4) and five regioisomeric dipyridyl-pyrene (5-9) conjugates were synthesized and characterized and their structures confirmed by single-crystal X-ray diffraction. The photophysical properties and related frontier orbital features of these compounds have been studied both experimentally and theoretically and demonstrate the dependence of the properties of the compounds on the position of substitution of the pyridyl moieties connecting to the pyrene core. It was found that the absorption spectra of 2- A nd 4-substituted pyrene derivatives display similar and weak influence on the S2 a? S0 excitations, whereas they are quite different from those of 1-substituted isomers. The emission spectra of 1- A nd 4-substituted pyrenes are quite similar, whereas those of 2-substituted isomers display the largest bathochromic shift. The 1,6-disubstituted compound 5 exhibits a near-unity emission quantum yield in solution, which is nearly three times higher than those of other regioisomeric dipyridyl-pyrenes. In addition, the tetrasubstituted 1,6-dipyridyl-3,8-di-n-butyl-pyrene (10) exhibits the highest solid-state quantum yield of 0.24 among all of the 10 pyridyl-pyrenes prepared in this study.
Porphyrins with exocyclic rings. Part 24. Synthesis and spectroscopic properties of pyrenoporphyrins, potential building blocks for porphyrin molecular wires
Gandhi, Virajkumar,Thompson, Michelle L.,Lash, Timothy D.
, p. 1787 - 1799 (2010)
Porphyrins with fused pyrene units have been prepared by '2+2' and '3+1' methodologies. Nitration of 1,2,3,6,7,8-tetrahydropyrene, followed by oxidation with DDQ, gave 4-nitropyrene and this condensed with ethyl isocyanoacetate in the presence of DBU or a phosphazene base to generate a pyrenopyrrole ethyl ester. Ester saponification and decarboxylation with KOH in ethylene glycol at 190 °C gave the parent pyreno[4,5-c]pyrrole and this was further condensed with 2 equiv of acetoxymethylpyrroles to afford the corresponding tripyrranes protected at the terminal positions with tert-butyl esters. In a one pot procedure, the ester protective groups were cleaved with TFA and following dilution with dichloromethane, '3+1' condensation with a pyrrole dialdehyde, and dehydrogenation with DDQ, the targeted pyrenoporphyrins were generated in good overall yields. A dialdehyde was also prepared from the pyrenopyrrole intermediate and this reacted to give an opp-dipyrenoporphyrin. The pyrenopyrrole ethyl ester reacted with dimethoxymethane in the presence of an acid catalyst to give a dipyrenopyrrolylmethane, and this was used to prepare an adj-dipyrenoporphyrin using the MacDonald '2+2' approach. The pyrenopyrrole dialdehyde was also used to prepare a porphyrin with fused pyrene and phenanthroline moieties. Although the UV-vis spectra of these new porphyrin systems are unexceptional, pyrenoporphyrins show many of the features necessary for the construction of porphyrin molecular wires.
The thermodynamic properties of 4,5,9,10-tetrahydropyrene and of 1,2,3,6,7,8-hexahydropyrene
Chirico, R. D.,Knipmeyer, S. E.,Nguyen, A.,Smith, N. K.,Steele, W. V.
, p. 729 - 761 (1993)
Measurements leading to the calculation of the ideal-gas thermodynamic properties are reported for 4,5,9,10-tetrahydropyrene (Chemical Abstracts registry number ) and 1,2,3,6,7,8-hexahydropyrene (registry number ).Experimental methods included combustion calorimetry, adiabatic heat-capacity calorimetry, vibrating-tube densitometry, comparative ebulliometry, inclined-piston gauge manometry, and differential-scanning calorimetry (d.s.c).Critical properties were estimated for both materials based on the measurement results.Standard entropies, enthalpies, and Gibbs free energies of formation were derived for the gases for selected temperatures between 380 K and 700 K.The property-measurement results reported here for 4,5,9,10-tetrahydropyrene and 1,2,3,6,7,8-hexahydropyrene are the first for these important intermediates in the (pyrene + hydrogen) reaction network.
Metallic Barium: A Versatile and Efficient Hydrogenation Catalyst
Stegner, Philipp,F?rber, Christian,Zenneck, Ulrich,Knüpfer, Christian,Eyselein, Jonathan,Wiesinger, Michael,Harder, Sjoerd
supporting information, p. 4252 - 4258 (2020/12/22)
Ba metal was activated by evaporation and cocondensation with heptane. This black powder is a highly active hydrogenation catalyst for the reduction of a variety of unactivated (non-conjugated) mono-, di- and tri-substituted alkenes, tetraphenylethylene, benzene, a number of polycyclic aromatic hydrocarbons, aldimines, ketimines and various pyridines. The performance of metallic Ba in hydrogenation catalysis tops that of the hitherto most active molecular group 2 metal catalysts. Depending on the substrate, two different catalytic cycles are proposed. A: a classical metal hydride cycle and B: the Ba metal cycle. The latter is proposed for substrates that are easily reduced by Ba0, that is, conjugated alkenes, alkynes, annulated rings, imines and pyridines. In addition, a mechanism in which Ba0 and BaH2 are both essential is discussed. DFT calculations on benzene hydrogenation with a simple model system (Ba/BaH2) confirm that the presence of metallic Ba has an accelerating effect.
Unraveling the Homologation Reaction Sequence of the Zeolite-Catalyzed Ethanol-to-Hydrocarbons Process
Chowdhury, Abhishek Dutta,Lucini Paioni, Alessandra,Whiting, Gareth T.,Fu, Donglong,Baldus, Marc,Weckhuysen, Bert M.
supporting information, p. 3908 - 3912 (2019/02/20)
Although industrialized, the mechanism for catalytic upgrading of bioethanol over solid-acid catalysts (that is, the ethanol-to-hydrocarbons (ETH) reaction) has not yet been fully resolved. Moreover, mechanistic understanding of the ETH reaction relies heavily on its well-known “sister-reaction” the methanol-to-hydrocarbons (MTH) process. However, the MTH process possesses a C1-entity reactant and cannot, therefore, shed any light on the homologation reaction sequence. The reaction and deactivation mechanism of the zeolite H-ZSM-5-catalyzed ETH process was elucidated using a combination of complementary solid-state NMR and operando UV/Vis diffuse reflectance spectroscopy, coupled with on-line mass spectrometry. This approach establishes the existence of a homologation reaction sequence through analysis of the pattern of the identified reactive and deactivated species. Furthermore, and in contrast to the MTH process, the deficiency of any olefinic-hydrocarbon pool species (that is, the olefin cycle) during the ETH process is also noted.
Highly efficient pyrene blue emitters for OLEDs based on substitution position effect
Jung, Mina,Lee, Jaehyun,Jung, Hyocheol,Kang, Seokwoo,Wakamiya, Atsushi,Park, Jongwook
, p. 42 - 49 (2018/05/24)
To investigate the effect of substitution position of the side group on a pyrene core, three derivatives having a triphenylbenzene group as a bulky side group at the 1,6-position, 4,9-position, and 1,8-position were successfully synthesized: 1,6-bis(5′-phenyl-[1,1':3′,1″-terphenyl]-4-yl)pyrene (1,6-DTBP), 4,9-bis(5′-phenyl-[1,1':3′,1″-terphenyl]-4-yl)pyrene (4,9-DTBP), and 1,8-bis(5′-phenyl-[1,1':3′,1″-terphenyl]-4-yl)pyrene (1,8-DTBP). The three synthesized materials showed excellent thermal stability with a high Tg of >140 °C and a high Td of >500 °C. Due to the highly twisted structure of 1,8-DTBP in the film state, the absolute photoluminescence quantum yield value was improved. Of the three synthesized materials used as an emitter in a non-doped organic light-emitting diode device, 1,8-DTBP showed highly efficient electroluminescence performance, with a luminance efficiency of 6.89 cd/A, power efficiency of 3.03 lm/W, and external quantum efficiency of 7.10% at 10 mA/cm2. In addition, 4,9-DTBP showed a deep-blue emission of CIE x, y (0.158, 0.063) suitable for HD-TV.
ORGANIC COMPOUND INCLUDING FUSED CORE MOIETY, ORGANIC OPTOELECTRIC DEVICE INCLUDING THE SAME AND DISPLAY
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Paragraph 0425; 0432; 0433, (2017/01/05)
The present invention relates to: an organic compound represented by a combination of chemical formula 1 and chemical formula 2; and an organic optoelectronic device and a display device comprising the organic compound. In chemical formulas, R1 to R5, R9 to R14, X, m and n are the same as described in the specification. Good electrical properties, light emitting properties, color properties, and the like can be obtained by employing the organic compound to the organic optoelectronic device.COPYRIGHT KIPO 2016
