1732-13-4Relevant articles and documents
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.
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.
Efficient Synthesis of 4,5,9,10-Tetrahydropyrene: A Useful Synthetic Intermediate for the Synthesis of 2,7-Disubstituted Pyrenes
Connor, Daniel M.,Allen, Scott D.,Collard, David M.,Liotta, Charles L.,Schiraldi, David A.
, p. 6888 - 6890 (1999)
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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.
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.
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.
