128-63-2Relevant articles and documents
Electron-Transfer-Induced Self-Assembly of a Molecular Tweezer Platform
Thakur, Khushabu,Wang, Denan,Mirzaei, Saber,Rathore, Rajendra
, p. 14085 - 14089 (2020)
The design and synthesis of a new molecular tweezer (T-tmp) with electron-rich pincers are reported. The stable monocationic radicals and self-assembled dimeric radicals of this molecular tweezer platform were prepared by chemical oxidative titration. With the aid of DFT calculations, it was found that the dimeric radicals with syn-syn-syn conformer has the most stable structure, with the hole primarily delocalized between parallel stacked pyrenyl groups.
Mono- and Diruthenium, Symmetrical and Unsymmetrical Complexes Bridged by Pyrene Derivatives: Experimental and Theoretical Studies
Zych, Dawid,Slodek, Aneta,Paj?k, Micha?,Krompiec, Stanis?aw,Spólnik, Grzegorz,Danikiewicz, Witold
, p. 3868 - 3877 (2017)
New mono- and diruthenium, symmetrical and unsymmetrical complexes, bridged by a new cyclometalating 1,3,6,8-tetra(4-substituted-2-pyridyl)pyrene derivative containing the solubilizing group 2,2-dimethylpropyloxy, with the terminal 4′-phenyl-2,2′:6′,2′′-terpyridine ligands containing diethylamine and a 2-ethynyl-9,9-dioctylfluorene moiety, were synthesized and thoroughly characterized. Thermal studies show that the obtained complexes retain high thermal stability. Spectroscopic studies show the metal-to-ligand charge-transfer excitation. Further, electrochemical studies show delocalization of the electronic charge (mixed valance). In addition, density functional theory and time-dependent density functional theory calculations have provided more detail about the structural properties and a deeper understanding of the experimental results. All of the obtained results show the considerable differences between the mono- and diruthenium and symmetrical and unsymmetrical complexes.
Tailoring the framework of organic small molecule semiconductors towards high-performance thermoelectric composites: Via conglutinated carbon nanotube webs
Yin, Xiaojun,Peng, Yuhao,Luo, Jiajia,Zhou, Xiaoyan,Gao, Chunmei,Wang, Lei,Yang, Chuluo
, p. 8323 - 8330 (2018)
Recently, the thermoelectric (TE) properties of single-walled carbon nanotubes (SWCNTs)/polymer semiconductor composites have been dramatically improved; however, there are no examples of SWCNTs/organic small molecule semiconductor (OSMS) composites as TE materials, although OSMSs are more attractive due to their exact structure, easy structure optimization, high purity for performance optimization, etc. In this work, four p-type OSMSs are designed and synthesized as p-type binders for application in SWCNT-doped composite films. The relationship between TE properties and the structure including the conjugated-backbone and peripheral substituents is investigated. Photophysical spectroscopic and scanning electron microscopic studies indicate that the variation of molecular geometries and hybrid ratios results in obvious changes in the morphologies, interfacial contacts and grain boundaries of the composite films, subsequently affecting the TE properties of the samples. Notably, the SWCNT/TCzPy (1:1)-based hybrid film exhibits the best performance with an average power factor of 108.4 ± 4.8 μW m-1 K-2, which is three times higher than that of SWCNT/TDOPAPy. The results demonstrate that fine tuning the π-extensions of the central core or peripheral substituents of organic semiconductors is a good strategy for designing high-performance p-type organic small molecule TE materials.
Furyl derivatives of pyrene: Efficient synthesis and relevant optical properties
Idzik, Krzysztof R.,Ledwon, Przemyslaw,Licha, Tobias,Kuznik, Wojciech,Lapkowski, Mieczyslaw,Frydel, Jaroslaw
, p. 55 - 61 (2014)
A series of various furyl derivatives of pyrene were synthesized by Stille cross-coupling procedure. Their structures were characterized by nuclear magnetic resonance, and elemental analysis. Optical properties of the synthesized materials as well as their energy levels were investigated by ultraviolet-visible absorption supported by fluorescence spectra. All of the studied compounds exhibit fluorescence with energy peaks dependent on the number of furyl substituents. Furthermore, quantum mechanical modeling method of obtained materials are studied. Experimental data are focused on quantum chemical calculations. Highest occupied molecular and lowest unoccupied molecular orbitals are delocalized uniformly on both pyrene core and furyl substituents. Furanyl-pyrene hybrids are potentially good materials for optical applications mainly due to their optical and charge transport properties, which are also desired for electronic applications.
Synthesis and fluorescence emission properties of 1,3,6,8-tetrakis(9H- fluoren-2-yl)pyrene derivative
Hu, Jian-Yong,Hiyoshi, Hidetaka,Do, Jung-Hee,Yamato, Takehiko
, p. 278 - 282 (2010)
A novel pyrene-based highly pure blue fluorescent and stable molecule, 1,3,6,8-tetrakis[9,9-bis(3-methylbutyl)-9Hfluoren- 2-yl]pyrene, was successfully synthesised via a Pd-catalysed Suzuki coupling reaction of 1,3,6,8- tetrabromopyrene with 2-[9,9-bis(3-methylbutyl)-9H-fluoren-2-yl]-4,4,5,5- tetramethyl[1,3,2]dioxaborolane. The photoproperties of this pyrene were examined in detail and these data indicated its potential application as blue-emitting materials in organic light-emitting diodes.
Ethynylpyrene Linked Benzocrown Ethers as Fluorescent Sensors for Metal Ions
Maeda, Hajime,Tanaka, Kazuhiro,Aratani, Mona,Segi, Masahito
, p. 762 - 772 (2019)
Substances containing ethynylpyrenes linked to either one or four benzocrown ethers were synthesized, and their absorption and fluorescence spectroscopic responses to metal ions were assessed. Addition of metal perchlorates to solutions of these substances promotes short wavelength shifts in their absorption and fluorescence maxima and increases in their fluorescence intensities. The magnitudes of the fluorescence intensity increases are dependent on the ring size and number of the crown ether and the nature of the metal cation. Association constants for complex formation were calculated using fluorescence intensity versus concentration data. Analysis using Job's plots showed that the substances containing one benzocrown ether moiety form 1:1 complexes with metal ions. Results of experiments employing repeated addition and removal of Mg(ClO4)2 demonstrate that the ON-OFF fluorescence response can be repeated at least three times. Results of molecular orbital calculations show that complexation with metal ions lowers the energies of both the π and π* levels of the ethynylpyrene moiety and that in some cases the vacant orbital on the metal becomes the LUMO of the complex. An explanation of the spectroscopic changes promoted by metal ions is proposed in terms of electrostatic repulsion and structural regulation.
Substituent effect of conjugated microporous polymers on the photocatalytic hydrogen evolution activity
Chen, Yu,Gao, Xiaomin,Jiang, Jia-Xing,Ma, Wenyan,Ren, Shi-Bin,Shu, Chang,Wang, Feng,Zeng, Jing Hui,Zhang, Chong
, p. 2404 - 2411 (2020)
The construction of a donor-acceptor (D-A) organic photocatalyst is a facile approach to improve photocatalytic performances because of the efficient separation of light-generated electrons and holes. The rational design of molecular skeletons and the selection of functional groups are of great importance to an organic photocatalyst with a high photocatalytic activity. Herein, we designed two D-A conjugated microporous polymers (CMPs) with different substituent groups of fluorine atoms and methyl groups on the acceptor unit of dibenzothiophene-dioxide (DBTDO). This study reveals that the introduction of fluorine atoms with strong electron-withdrawing ability onto the acceptor unit can further enhance the electron acceptability of the DBTDO unit, leading to the efficient separation of light-generated electrons and holes, while the introduction of methyl with electron-pushing ability decreases the electron acceptability of the acceptor unit, suppressing the separation of light-generated charge carriers. As a result, the polymer PyDF with fluorine atoms shows an excellent photocatalytic activity compared to PyDM with methyl groups. Under UV/Vis light irradiation, PyDF shows an attractive photocatalytic hydrogen generation rate of 18.93 mmol h-1 g-1, which is much higher than that of PyDM (3.96 mmol h-1 g-1), implying that the functional group acts as a vital role in the catalytic activity of polymer semiconducting photocatalysts.
Two Li-Zn cluster-based metal-organic frameworks: Strong H2/CO2 binding and high selectivity to CO2
Huang, Yong-Liang,Zhong, Di-Chang,Jiang, Long,Gong, Yun-Nan,Lu, Tong-Bu
, p. 705 - 708 (2017)
Two metal-organic frameworks (MOFs) {(Me2NH2)[ZnLi(PTCA)(H2O)]}nn{3DMFC4H8O2 4H2O} (1) and {(Me2NH2)[ZnLi(PTCA)]}nn{3DMF 5H2O} (2) have been constructed from Li-Zn clusters and pyrene-1,3,6,8-tetracarboxylic acid (H4PTCA) under solvothermal conditions. Gas sorption measurements have revealed that the pore of desolvated 2 (2d) can strongly interact with H2 and CO2, with high H2 and CO2 adsorption heats of 15.3 and 51.9 kJ/mol, respectively. Furthermore, 2d can selectively adsorb CO2 over N2and CH4, with high adsorption selectivity of CO2/N2 and CO2/CH4.
Effects of substituents on silicon atoms upon absorption and fluorescence properties of 1,3,6,8-tetrakis(silylethynyl)pyrenes
Maeda, Hajime,Shoji, Tomokazu,Segi, Masahito
, p. 4372 - 4376 (2017)
Synthesis, UV–vis absorption, and fluorescence spectroscopic properties of 1,3,6,8-tetrakis(silylethynyl)pyrenes 2–10 were studied. Absorption maxima of CH2Cl2 solutions of these compounds appeared at 437–445 nm, and molar absorption coefficients (ε) of most of these compounds exceeded 105 L mol?1 cm?1. Fluorescence emissions measured in dilute CH2Cl2 solutions are observed in visible region, and their intensities remarkably increased compared with that of pyrene. Fluorescence spectra obtained from concentrated CH2Cl2 solutions exhibited broad excimer emissions when steric bulk of substituents on silicon atoms is sufficiently low. Molecular orbital calculations indicated that HOMO-LUMO energy gap decreased with increasing the number of phenyl groups on silicon atoms, and that the silyl groups act as electron-donating groups to tetraethynylpyrene core. Resonances in 29Si NMR spectra shifts to upfield with increasing the number of phenyl groups on silicon atoms due to the shielding effect of phenyl groups.
Synthesis, absorption, and fluorescence-emission properties of 1,3,6,8-tetraethynylpyrene and its derivatives
Venkataramana, Gandikota,Sankararaman, Sethuraman
, p. 4162 - 4166 (2005)
The synthesis of several 1,3,6,8-tetraethynylpyrene derivatives is reported. The effect of extended acetylenic conjugation on their absorption and fluorescence-emission properties is studied. Significant bathochromic shifts of both the absorption and fluorescence emission bands are observed. These derivatives emit fluorescence in the visible (400-550 nm) region. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
Isolation and X-ray structural characterization of tetraisopropylpyrene cation radical
Banerjee, Moloy,Vyas, Vijay S.,Lindeman, Sergey V.,Rathore, Rajendra
, p. 1889 - 1891 (2008)
A practical synthesis of 1,3,6,8-tetraisopropylpyrene and the isolation and X-ray structural characterization of its monomeric cation radical salt are described. The Royal Society of Chemistry.
The optical properties and quantum chemical calculations of thienyl and furyl derivatives of pyrene
Idzik, Krzysztof R.,Cywiński, Piotr J.,Kuznik, Wojciech,Frydel, Jaroslaw,Licha, Tobias,Ratajczyk, Tomasz
, p. 22758 - 22769 (2015)
A detailed electrochemical, photophysical and theoretical study is presented for various new thienyl and furyl derivatives of pyrene. Their optical properties are described based on UV-VIS absorption and both steady-state and time-resolved fluorescence spectroscopy. DFT and TDDFT calculations are also presented to support experimental data. The calculations results show that HOMO-LUMO orbitals are delocalized uniformly between aromatic core and aryl substituents. Good electrochemical stability of thienyl and furyl hybrids of pyrene confirm their potential application for light emitting electrochemical cells or spintronics mainly due to their beneficial optical and charge transport properties in electrochromic devices. In order to demonstrate this potential, an OLED device is presented. Synthesized compounds included in this OLED device both facilitate electron transport and act as a light emitting layer.
Pyrene-containing conjugated organic microporous polymers for photocatalytic hydrogen evolution from water
Mohamed, Mohamed Gamal,Elsayed, Mohamed Hammad,Elewa, Ahmed M.,EL-Mahdy, Ahmed F. M.,Yang, Cheng-Han,Mohammed, Ahmed A. K.,Chou, Ho-Hsiu,Kuo, Shiao-Wei
, p. 2229 - 2241 (2021)
Photoactive conjugated microporous polymers (CMPs) are emerging as porous materials capable of mediating the photocatalytic evolution of H2from water. In this study, we synthesized three pyrene-based CMPs (Py-F-CMP, Py-TPA-CMP, Py-TPE-CMP) through Sonogashira-Hagihara cross-couplings of 1,3,6,8-tetraethynylpyrene (Py-T, as a common monomer building block) with 2,7-dibromo-9H-fluorene (F-Br2), tris(4-bromophenyl)amine (TPA-Br3), and 1,1,2,2-tetrakis(4-bromophenyl)ethene (TPE-Br4), respectively, in the presence of Pd(PPh3)4in DMF/Et3N. We then characterized the chemical structures, crystallinities, thermal stabilities, surface morphologies, and porosities of these three new CMPs. Brunauer-Emmett-Teller (BET) analyses and tests of photocatalytic H2production revealed that Py-TPA-CMP displayed the highest BET surface area (454 m2g?1), highest total pore volume (0.28 cm3g?1), highest H2evolution rate (19?200 μmol h?1g?1), and highest apparent quantum yield (15.3%) when compared with those of Py-F-CMP, Py-TPE-CMP, and other organic porous materials.
Modulation of Gas Sorption Properties through Cation Exchange within an Anionic Metal–Organic Framework
Huang, Yong-Liang,Jiang, Long,Lu, Tong-Bu
, p. 780 - 785 (2016)
A novel 3D anionic metal–organic framework (MOF) of (Me2NH2)4[Ni8(PTCA)4(μ3-OH)4(H2O)4](DMF)5(H2O)13 (H4PTCA=pyrene-1,3,6,8-tetracarboxylic acid) has been synthesized, in which Me2NH2 + can be exchanged by Li+ ions. The results of gas sorption measurements indicate that the desolvated MOFs both before and after Li+ exchange show highly selective adsorption for CO2 over CH4 and N2 gases, and the Li+-exchanged MOF exhibits enhanced CO2, CH4, and H2 storage properties.
Heteroporous bifluorenylidene-based covalent organic frameworks displaying exceptional dye adsorption behavior and high energy storage
Chen, Tao,El-Mahdy, Ahmed F. M.,Kuo, Shiao-Wei,Wang, Hao-Xin,Yamauchi, Yusuke,Zakaria, Mohamed Barakat
, p. 25148 - 25155 (2020)
In this study we performed one-pot polycondensations of BFTB-4CHO with PyTA-4NH2, BFTB-4NH2, and BCTA-4NH2 to prepare the bifluorenylidene-based covalent organic frameworks (COFs) BFTB-PyTA, BFTB-BFTB, and BFTB-BCTA, respectively. These three COFs possessed extremely high thermal stabilities, excellent crystallinities, and high specific surface areas. The BFTB-PyTA COF featured pores of a single size, whereas the BFTB-BFTB and BFTB-BCTA COFs had dual porosities. The COFs were exceptional adsorbers of the small dye molecule rhodamine B (RhB) in water; the maximum adsorption capacities reached as high as 2127 mg g-1, outpacing those of all previously reported COFs, conjugated polymers, activated carbons, and other common nanoporous adsorbents. In addition, our COFs reached up to 99.2% of their maximum adsorption capabilities very rapidly (within 5 min). Furthermore, these COFs displayed good performance when used in electrodes for supercapacitors, with high stability after 2000 cycles. The superior adsorption efficiencies, ultrafast kinetics, and excellent reusability endow such COFs with tremendous potential for use as materials for removing RhB-and, presumably, other organic pollutants-from wastewater.
Photophysical properties of 1,3,6,8-tetraarylpyrenes and their cation radicals
Vyas, Vijay S.,Lindeman, Sergey V.,Rathore, Rajendra
, p. 209 - 218 (2019)
The synthesis of 1,3,6,8-tetraaryl substituted pyrenes is described. The substituents on the aryl groups influence the optoelectronic properties of the pyrene core indicating a strong coupling between the aryl groups and the pyrene core. Electronic absroption spectra of the cation radicals generated in solution by the single electron oxidation of pyrenes reaffirmed the coupling of the aryl rings with the pyrene. The aryl groups at 1,3,6,8-positions completely inhibit the π-stacking of pyrene core in solution. Crystal structure of the cation radical salt of tetraphenyl shows charge delocalization between neutral pyrene unit and two cationic pyrene cores. Complete inhibition of the pyrene core stacking is observed in the solid state of cation radical when the dendritic pentaphenyl groups surround the pyrene core.
Synthesis and optical properties of various thienyl derivatives of pyrene
Idzik, Krzysztof R.,Licha, Tobias,Lukes, Vladimir,Rapta, Peter,Frydel, Jaroslaw,Schaffer, Mario,Taeuscher, Eric,Beckert, Rainer,Dunsch, Lothar
, p. 153 - 160 (2014)
A series of various thienyl derivatives of pyrene were synthesized by Stille cross-coupling procedure. Their structures were characterized by 1H NMR, 13C NMR and elemental analysis. The spectroscopic characteristics were investigated by UV-vis absorption and fluorescence spectra. Based on quantum chemical calculations, the energy levels of investigated molecules with respect to the pyrene molecule were also discussed.
Cobalt metal organic framework material based on tetra(pyrazolyl)pyrene ligand as well as preparation method and application thereof
-
Paragraph 0022-0023; 0033, (2021/04/10)
The invention discloses a cobalt metal organic framework material based on tetra(pyrazolyl)pyrene ligand as well as a preparation method and application thereof, belonging to the technical field of crystalline materials. The chemical molecular formula of the material is Co(H4TPP)(CH3COO)2(H2O)(CH3CN)2, wherein H4TPP is an organic ligand, namely 1,3,6,8-tetra(1H-pyrazol-4-yl)pyrene. The preparation method of the metal organic framework comprises the following step: under a closed condition, carrying out a solvothermal reaction on the organic ligand 1,3,6,8-tetra(1H-pyrazol-4-yl)pyrene and cobalt nitrate in a mixed solution of N,N-dimethylformamide, acetic acid and acetonitrile to obtain a crystal. The metal organic framework material shows potential application value of selectively adsorbing and separating carbon dioxide, methane and nitrogen.
(E)-1,2-Diphenylethene-based conjugated nanoporous polymers for a superior adsorptive removal of dyes from water
El-Mahdy, Ahmed F. M.,Saber, Ahmed F.
supporting information, p. 21834 - 21843 (2021/12/13)
Conjugated microporous polymers (CMPs) as prospective adsorbents for organic pollutant treatments are extremely appealing for both basic and applied kinds of research due to their simplicity, high performance, low cost, and processing under ambient conditions. However, the development of CMPs having excellent pollutant adsorption behaviour is still challenging. Herein, we described the targeted synthesis of a series of (E)-1,2-diphenylethene-based CMPs - BIPE-BIPE, BIPE-Py, and BIPE-TPT CMPs - via [4 + 4] and [4 + 3] Suzuki-Miyaura polymerizations of the novel (E)-1,2-bis(3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethene (BITPE-4Bpin) with 1,2-bis(3,5-dibromophenyl)ethene (BIPE-4Br), 1,3,6,8-tetrabromopyrene (Py-4Br), and 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (TPT-3Br), respectively. The porosities, chemical structures, and morphologies of the three CMPs were studied. The synthesized CMPs displayed high BET surface areas (up to 1400 m2 g-1) and outstanding thermal stabilities (up to a Td10 of 604 °C and char yield of 81 wt%). In addition, the as-prepared CMPs showed an extraordinarily high adsorption capacity for the organic dye rhodamine B (RhB) from water; the maximum adsorption capacity for RhB was 1027 mg g-1. Interestingly, our CMPs exhibited good recyclability and quickly attained 99.6% of their maximal adsorption capacity within 3 min. Our CMPs with the excellent adsorption behaviour could be good materials for water treatment and purification applications.
