- Synthesis and properties of oligonucleotides involving a perylene unit linked to a 2′-deoxyribose residue
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We report here the synthesis and binding properties of oligonucleotides involving a perylene unit linked to the anomeric position of a 2′-deoxyribose residue. Both anomers were separated and incorporated separately at either the 5′-end or the internal position of a pyrimidine sequence. In any case the presence of the perylene unit stabilizes the complexes formed with either the single or the double-stranded target.
- Aubert, Yves,Asseline, Ulysse
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- Synthesis, photophysical and electrochemical properties of perylene dyes
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Perylene dyes comprising: (i) 4-alkoxyphenylamino moiety in the 9-position as a strong donating group, (ii) cyanoacrylic acid as electron acceptor and anchoring group and (iii) a triple bond as short and rigid linker between perylene core and the acceptor group have been successfully synthesized. Their photophysical (i.e. absorption and emission spectra, molar extinction coefficients, fluorescence quantum yields and lifetime measurements) and electrochemical properties were investigated. The dyes display intense absorption in the visible exhibit high molar absorption coefficients making them good light harvesting materials for ss-DSCs.
- Torres, érica,Berberan-Santos, Mário Nuno,Brites, Maria Jo?o
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- Oxidative cyclodehydrogenation of a perylene derivative: different reagents give different products
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An efficient synthesis of 3-fluoroterrylene, a promising molecular nanoprobe for single electron optical sensing, is described. The key synthetic steps comprised the palladium-catalysed cross-coupling reaction of 3-bromoperylene and 4-fluoronaphthalene-1-boronic acid pinacol ester to give 3-(4-fluoronaphthalen-1-yl)perylene, followed by oxidative cyclodehydrogenation to give selectively either 3-fluoroterrylene or its isomer 10-fluorobenzo[4,5]indeno[1,2,3-cd]perylene. The selectivity of the Scholl oxidation under AlCl3/chlorobenzene or DDQ/TfOH conditions was confirmed by 19F NMR.
- Markoulides, Marios S.,Venturini, Chiara,Neumeyer, David,Gourdon, André
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- Photooxygenation of alkynylperylenes. Formation of dibenzo[jk,mn] phenanthrene-4,5-diones
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(Chemical Equation Presented) 3-(1-Alkynyl)perylenes undergo oxygenation when subjected to irradiation with visible light under aerated conditions. The structures of novel oxygenated products formed in this manner are assigned as regioisomeric dibenzo[jk,
- Maeda, Hajime,Nanai, Yasuaki,Mizuno, Kazuhiko,Chiba, Junya,Takeshima, Sakiko,Inouye, Masahiko
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- Communication of Bichromophore Emission upon Aggregation – Aroyl-S,N-ketene Acetals as Multifunctional Sensor Merocyanines
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Aroyl-S,N-ketene acetal-based bichromophores can be readily synthesized in a consecutive three-component synthesis in good to excellent yields by condensation of aroyl chlorides and an N-(p-bromobenzyl) 2-methyl benzothiazolium salt followed by a Suzuki coupling, yielding a library of 31 bichromophoric fluorophores with substitution pattern-tunable emission properties. Varying both chromophores enables different communication pathways between the chromophores, exploiting aggregation-induced emission (AIE) and energy transfer (ET) properties, and thus, furnishing aggregation-based fluorescence switches. Possible applications range from fluorometric analysis of alcoholic beverages to pH sensors.
- Biesen, Lukas,May, Lars,Nirmalananthan-Budau, Nithiya,Hoffmann, Katrin,Resch-Genger, Ute,Müller, Thomas J. J.
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supporting information
p. 13426 - 13434
(2021/08/06)
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- Compound containing perylene and fluorobenzene as well as preparation method and application of compound
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The invention discloses a compound containing perylene and fluorobenzene. The structure of the compound is shown as a formula 1, the preparation method of the compound comprises the following specificsteps: (1) reacting perylene with N-bromo succinimide to prepare a compound I; (2) reacting the compound I with bis (pinacolato) diboron to obtain a compound II; (3) reacting the compound II with 2,3, 5, 6-tetrafluoro-1, 4-dibromobenzene to prepare a compound III; and (4) reacting the compound III with pentafluorophenylboronic acid to obtain a compound IV. Based on good structural modification and various photoelectric properties of perylene and perylene series compounds, high-color-purity green-light LED devices can be prepared, and huge application potential in the aspect of green fluorescent powder for white-light LEDs is achieved.
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Paragraph 0010; 0034-0037; 0044-0047; 0054-0057
(2021/01/21)
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- Electron Push-Pull Effects on Intramolecular Charge Transfer in Perylene-Based Donor-Acceptor Compounds
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A series of asymmetric donor-acceptor (D-A) perylene-based compounds, 3-(N,N-bis(4′-(R)-phenyl)amino)perylene (Peri-DPA(R)), were successfully prepared to explore their intramolecular charge transfer (ICT) properties. To induce ICT between the donor and acceptor, diphenylamine (DPA) derivatives (electron donor units) with the same functional groups (R = CN, F, H, Me, or OMe) at both para positions were linked to the C-3 position of perylene to produce five Peri-DPA derivatives. A steady-state spectroscopy study on Peri-DPA(R)s exhibited a progressively regulated ICT trend consistent with the substituent effect as it progressed from the electron-withdrawing group to the electron-donating group. In particular, a comparative study using a D-A-D (donor-acceptor-donor) system demonstrated that not only the electron push-pull substituent effect but also subunit combinations influence photophysical and electrochemical properties. The different ICT characters observed in Lippert-Mataga plots of D-A(CN) and D-A-D(CN) (CN-substituted D-A and D-A-D) led to the investigation on whether ICT emission of two systems with differences in subunit combinations is of the same type or of a different type. The femtosecond transient absorption (fs-TA) spectroscopic results provided direct evidence of ICT origin and confirmed that D-A(CN) and D-A-D(CN) exhibited the same transition mix of ICT (from donor to acceptor) and reverse ICT (rICT, from arylamine to CN unit). Density functional theory (DFT)/TD-DFT calculations support the presence of ICT for all five compounds, and the experimental observations of rICT presented only for CN-substituted compounds.
- Ahn, Mina,Kim, Min-Ji,Cho, Dae Won,Wee, Kyung-Ryang
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p. 403 - 413
(2020/12/23)
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- Efficient Triplet–Triplet Annihilation Upconversion in Solution and Hydrogel Enabled by an S-T Absorption Os(II) Complex Dyad with an Elongated Triplet Lifetime
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A new Os(II) complex dyad featuring direct singlet-to-triplet (S-T) absorption and intramolecular triplet energy transfer (ITET) with lifetime up to 7.0 μs was designed to enhance triplet energy transfer efficiency during triplet–triplet annihilation upconversion (TTA-UC). By pairing with 9,10-bis(phenylethynyl)anthracene (BPEA) as a triplet acceptor, intense upconverted green emission in deaerated solution was observed with unprecedented TTA-UC emission efficiency up to 26.3% (with a theoretical maximum efficiency of 100%) under photoexcitation in the first biological transparency window (650–900 nm). Meanwhile, a 7.1% TTA-UC emission efficiency was acquired in an air-saturated hydrogel containing the photosensitizer and a newly designed hydrophilic BPEA derivative. This ITET mechanism would inspire further development of a highly efficient TTA-UC system for biological fields and renewable energy production.
- Wei, Yaxiong,Li, Yuanming,Li, Zefeng,Xu, Xinsheng,Cao, Xiaosong,Zhou, Xiaoguo,Yang, Chuluo
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supporting information
p. 19001 - 19008
(2021/12/17)
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- Red or near-infrared light operating negative photochromism of a binaphthyl-bridged imidazole dimer
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The development of red or near-infrared light (NIR) switchable photochromic molecules is required for an efficient utilization of sunlight and regulation of biological activities. While the photosensitization of photochromic molecules to red or NIR light has been achieved by a two-photon absorption process, the development of a molecule itself having sensitivity to red or NIR light has been now a challenging study. Herein, we developed an efficient molecular design for realizing red or NIR-light-responsive negative photochromism based on binaphthyl-bridged imidazole dimers. The introduction of electron-donating substituents shows the red shift of the absorption band at the visible-light region because of the contribution of a charge-transfer transition. Especially, the introduction of a di(4-methoxyphenyl)amino group (TPAOMe) and a perylenyl group largely shifts the absorption edge of the stable colored form to 900 nm. In addition, because the absorption band of one of the derivatives substituted with TPAOMe covers the whole visible-light region, the colored form shows a neutral gray color. Upon red (660 nm) or NIR-light (790 nm) irradiation, we observed the negative photochromic reaction from the stable colored form to the metastable colorless form. Therefore, the substituted binaphthyl-bridged imidazole dimers constitute the attractive photoswitches within a biological window.
- Kometani, Aya,Inagaki, Yuki,Mutoh, Katsuya,Abe, Jiro
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p. 7995 - 8005
(2020/05/27)
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- Intersystem crossing: via charge recombination in a perylene-naphthalimide compact electron donor/acceptor dyad
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In order to study the relationship between the molecular structures of compact electron donor/acceptor dyads and the spin-orbit charge transfer intersystem crossing (SOCT-ISC) efficiency, we prepared a perylene (Pery)-naphthalimide (NI) dyad, in which the Pery unit is the electron donor and the NI unit is the electron acceptor, where the two units adopt an almost orthogonal geometry. The photophysical properties of the dyad were studied with steady state and femtosecond/nanosecond transient absorption (fs TA and ns TA) spectroscopies, time resolved electron paramagnetic resonance (TREPR) spectroscopy and DFT computations. A very weak charge transfer (CT) absorption band was observed, but the fluorescence of the Pery unit is strongly quenched. Upon selective excitation into the NI unit, the fast intramolecular CS process (10 ps) occurs, followed by ISC and only the 3Pery? state is observed; whereas upon selective photoexcitation into the perylene unit, an ultrafast charge separation (0.66 ps) is observed, followed by SOCT-ISC (8 ns) to populate the 3Pery? state. Moreover, the perylene radical cation is also observed on the ns timescale, presumably formed by intermolecular charge transfer. The lifetime of the 3Pery triplet state was determined to be τT = 214 μs with ns TA spectroscopy. The singlet oxygen quantum yield was measured as ΦΔ = 80%, although the potential energy curve of the torsion between the donor and acceptor is shallow. The SOCT-ISC mechanism was confirmed by TREPR spectroscopy. The dyad was used as a triplet photosensitizer for the generation of delayed fluorescence (luminescence lifetime τDF = 57.3 μs). This journal is
- Bussotti, Laura,Di Donato, Mariangela,Doria, Sandra,El-Zohry, Ahmed M.,Foggi, Paolo,Imran, Muhammad,Matt, Clemens,Mohammed, Omar F.,Taddei, Maria,Weber, Stefan,Zhao, Jianzhang
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supporting information
p. 8305 - 8319
(2020/07/14)
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- Highly effective near-infrared activating tripleta-triplet annihilation upconversion for photoredox catalysis
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Organic triplet-triplet annihilation upconversion (TTA-UC) materials have considerable promise in areas as broad as biology, solar energy harvesting, and photocatalysis. However, the development of highly efficient near-infrared (NIR) light activatable TTA-UC systems remains extremely challenging. In this work, we report on a method of systematically tailoring an annihilator to attain such outstanding systems. By chemical modifications of a commonly used perylene annihilator, we constructed a family of perylene derivatives that have simultaneously tailored triplet excited state energy (T1) and singlet excited state energy (S1), two key annihilator factors to determine TTAUC performance. Via this method, we were able to tune the TTAUC system from an endothermic type to an exothermic one, thus significantly elevating the upconversion performance of NIR light activatable TTA upconversion systems. In conjunction with the photosensitizer PdTNP (10 μM), the upconversion efficiency using the optimal annihilator (100 μM) identified in this study was measured to be 14.1% under the low-power density of NIR light (100 mW/cm2, 720 nm). Furthermore, using such a low concentration of perylene derivative, we demonstrated that the optimal TTA-UC pair developed in our study can act as a highly effective light wavelength up-shifter to enable NIR light to drive a photoredox catalysis that otherwise requires visible light. We found that such an NIR driven method is highly effective and can even surpass directly visible light driven photoredox catalysis. This method is important for photoredox catalysis as NIR light can penetrate much deeper in colored photoredox catalysis reaction solutions, especially when done in a large-scale manner. Furthermore, this TTA-UC mediated photoredox catalysis reaction is found to be outdoor sunlight operable. Thus, our study provides a solution to enhance NIR activatable organic upconversion and set the stage for a wide array of applications that have previously been limited by the suboptimal efficiency of the existing TTA upconversion materials.
- Huang, Ling,Wu, Wenting,Li, Yang,Huang, Kai,Zeng, Le,Lin, Wenhai,Han, Gang
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supporting information
p. 18460 - 18470
(2020/11/17)
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- Synthesis of Perylene-Tagged Internal and External Electron Donors for Magnesium Dichloride Supported Ziegler-Natta Catalysts
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We report on the synthesis of three perylene-tagged electron donors representing three major types- phthalates, diethers, and alkoxysilanes - which are of importance for the subsequent studies of MgCl 2 -supported Ziegler-Natta catalysts by means of laser scanning confocal fluorescence microscopy. The obtained products were unambiguously characterized, including by X-ray crystal structure analysis; their photophysical properties (absorption and emission spectra) were investigated as well. Additionally, a reliable and convenient protocol for the multigram synthesis of the required starting material - 3-bromoperylene (PerBr) - was developed. The key step of this method was synthesis of trialkylsilyl-substituted perylenes, which were further separated by means of flash chromatography followed by conversion of the isolated 3-trialkylsilyl-substituted product to PerBr.
- Guzeev, Bogdan A.,Mladentsev, Dmitry Y.,Sharikov, Mikhail I.,Goryunov, Georgy P.,Uborsky, Dmitry V.,Voskoboynikov, Alexander Z.
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p. 1399 - 1407
(2019/03/07)
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- Spin-Allowed Transitions Control the Formation of Triplet Excited States in Orthogonal Donor-Acceptor Dyads
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Reliance on triplet excited states (triplets) of molecules with heavy atoms, such as precious metals, limits their potential in technological applications. We envision that triplets of π-conjugated organic molecules could play bigger roles; however, their production without heavy atoms remains challenging. The direct, spin-forbidden conversion of singlet charge-separated states to triplets in an electron donor-acceptor (D-A) pair is a promising approach. Here, using a series of orthogonal D-A type boron dipyrromethene (BODIPY) derivatives as a model system, we show that the formation of triplets is largely controlled by the spin-allowed transitions. Yet, this spin-forbidden process can still proceed much faster than ordinary intersystem crossing between (π π*) states under favorable conditions because of stronger spin-orbit coupling. Our findings reveal a clear physical basis for this spin-forbidden process and provide guidelines for future molecular designs exploiting the process. Production of triplet excited states of π-conjugated organic molecules in high yields without using heavy atoms remains challenging. The direct formation of triplet excited states from singlet charge-separated states is a promising approach. Here, we show that spin-allowed electron-transfer reactions largely control such a formation, yet the spin-forbidden transition can outcompete the spin-allowed transitions under favorable conditions because of stronger spin-orbit coupling. Triplet excited states (triplets) serve as key intermediates in critical technologies and processes ranging from organic synthesis to biomedicine to molecular electronics. Production of triplets of π-conjugated organic molecules without heavy atoms remains challenging. Spin-orbit, charge-transfer intersystem crossing (SOCT-ISC) directly converts singlet charge-separated states to triplets in an electron donor-acceptor (D-A) pair. Here, using a series of orthogonal D-A type boron dipyrromethene (BODIPY) derivatives as a model system, we show that the formation of triplets is largely controlled by the spin-allowed transitions rather than by SOCT-ISC. Yet, the SOCT-ISC process can still proceed much faster than ordinary ISC between (π π*) states because the spin-orbit coupling of SOCT-ISC is 2 orders of magnitude stronger. We further show that such a process can produce triplets in a non-triplet-forming molecule, perylene. Our findings reveal a clear physical basis for this spin-forbidden process and provide guidelines for future molecular designs exploiting the process.
- Buck, Jason T.,Boudreau, Andrew M.,DeCarmine, André,Wilson, Reid W.,Hampsey, James,Mani, Tomoyasu
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supporting information
p. 138 - 155
(2018/10/24)
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- Templated Chromophore Assembly on Peptide Scaffolds: A Structural Evolution
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The use of a template that bears pre-programmed receptor sites for selectively accommodating chromophores at given positions is an attractive approach for engineering artificial-light-harvesting systems. Indulging this line of thought, this work tackles the creation of tailored antenna architectures with yellow, red and blue chromophores, exploiting three dynamic covalent reactions simultaneously, namely disulfide exchange, acyl hydrazone, and boronic ester formations. The effect of various structural modifications, such as the chromophores as well as their spatial organization (distance, orientation, order) on the energy transfer within the antennas was studied by means of steady-state UV/Vis absorption and fluorescence spectroscopies. This systematic study allowed for a significant improvement of the energy-transfer efficiencies to a noticeable 22 and 15 % for the yellow and red donors, respectively, across the chromophores to the blue acceptor. Metadynamics simulations suggested that the conformational properties of the antennas are driven by intramolecular chromophoric stacking interactions that, upon forcing the α-helix to fold on itself, annul any effects deriving from the programming of the spatial arrangement of the receptor sides in the peptide backbone.
- Rocard, Lou,Wragg, Darren,Jobbins, Samuel Alexander,Luciani, Lorenzo,Wouters, Johan,Leoni, Stefano,Bonifazi, Davide
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supporting information
p. 16136 - 16148
(2018/10/15)
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- Effect of thiophene substitution on the intersystem crossing of arene photosensitizers
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The effect of thienyl substitution on the intersystem crossing (ISC) of a few arenes was studied using steady state and time-resolved transient absorption and emission spectroscopies, as well as DFT/TDDFT computations. We found that the phenyl and thienyl substituents generally induce red-shifted absorptions for the chromophores, and the DFT/TDDFT computations show that the red-shifted absorption and emission are due to the increased HOMO and the reduced LUMO energy levels. Nanosecond transient absorption spectra indicate the formation of a triplet state, the triplet state lifetime is up to 282 μs, and the singlet oxygen quantum yields (ΦΔ) are up to 60%. DFT/TDDFT computations indicate that introducing the thienyl substituent alters the relative singlet/triplet excited state energy levels, and the energy level-matched S1/T2 states are responsible for the enhanced ISC of the thienyl compounds. This information is useful for the design of heavy atom-free triplet photosensitizers and for the study of the fundamental photochemistry of organic compounds.
- Sadiq, Farhan,Zhao, Jianzhang,Hussain, Mushraf,Wang, Zhijia
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p. 1794 - 1803
(2018/11/23)
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- Reliable and reproducible separation of 3,9-and 3,10-dibromoperylenes and the photophysical properties of their alkynyl derivatives
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We developed a reliable and reproducible method for the separation of 3,9-dibromoperylene and 3,10-dibromoperylene resulting from bromination of perylene by using sequential and repeated recrystallization. Because of the unprecedented purities of the dibromoperylenes, they exhibit the high-est melting temperatures so far reported. In addition, various alkynylperylenes were prepared from the dibromoperylenes, and we investigated the photophysical characteristics of these alkynyl derivatives in detail.
- Hayashi, Koichiro,Inouye, Masahiko
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p. 4334 - 4337
(2018/08/28)
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- Metal-free reductive coupling of CO and CN bonds driven by visible light: Use of perylene as a simple photoredox catalyst
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Perylene, a simple polycyclic aromatic hydrocarbon, was used as a photoredox catalyst to enable the reductive coupling reaction of aromatic aldehydes, ketones, and an imine under visible-light irradiation using a white LED.
- Okamoto, Shusuke,Kojiyama, Keita,Tsujioka, Hiroki,Sudo, Atsushi
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supporting information
p. 11339 - 11342
(2016/09/23)
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- Enhanced Triplet-Triplet Energy Transfer and Upconversion Fluorescence through Host-Guest Complexation
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Perylene-tethered pillar[5]arenes and C60-boron-dipyrromethene (BODIPY) dyads were synthesized acting as emitters and organic triplet photosensitizers, respectively, for the purpose of improving the efficiency of triplet-triplet annihilation upconversion (TTA-UC). The photophysical properties of the sensitizers (guests) and the emitters (hosts) were not greatly influenced by the chemical modifications except for a notable decrease in the fluorescence quantum yields of the perlyene emitters due to the high local concentration. The perylene-tethered pillar[5]arenes form stable 1:1 complexes with a nitrile-bearing C60-BODIPY dyad, showing association constants as high as 4.0 × 104 M-1. Through host-guest complexation, the efficiencies of both triplet-triplet energy transfer and TTA were significantly enhanced, which overcompensated for the loss of the fluorescence quantum yield of the emitters (hosts). Thus, an improved TTA-UC efficiency of 3.2% was observed even at a diluted concentration of 6 × 10-5 M, demonstrating for the first time the effectiveness of the supramolecular motif for enhancing TTA-UC without varying the inherent photophysical properties of sensitizers and emitters.
- Fan, Chunying,Wu, Wanhua,Chruma, Jason J.,Zhao, Jianzhang,Yang, Cheng
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supporting information
p. 15405 - 15412
(2016/12/09)
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- Perylene-derived triplet acceptors with optimized excited state energy levels for triplet-triplet annihilation assisted upconversion
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A series of perylene derivatives are prepared as triplet energy acceptors for triplet-triplet annihilation (TTA) assisted upconversion. The aim is to optimize the energy levels of the T1 and S1 states of the triplet acceptors, so that the prerequisite for TTA (2ET1 > E S1) can be better satisfied, and eventually to increase the upconversion efficiency. Tuning of the energy levels of the excited states of the triplet acceptors is realized either by attaching aryl groups to perylene (via single or triple carbon-carbon bonds), or by assembling a perylene-BODIPY dyad, in which the components present complementary S1 and T 1 state energy levels. The S1 state energy levels of the perylene derivatives are generally decreased compared to perylene. The anti-Stokes shift, TTA, and upconversion efficiencies of the new triplet acceptors are improved with respect to the perylene hallmark. For the perylene-BODIPY dyads, the fluorescence emission was substantially quenched in polar solvents. Moreover, we found that extension of the π-conjugation of BODIPY energy donor significantly reduces the energy level of the S1 state. Low S1 state energy level and high T1 state energy level are beneficial for triplet photosensitizers.
- Cui, Xiaoneng,Charaf-Eddin, Azzam,Wang, Junsi,Le Guennic, Boris,Zhao, Jianzhang,Jacquemin, Denis
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p. 2038 - 2048
(2014/04/03)
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- High quantum yield molecular bromine photoelimination from mononuclear platinum(IV) complexes
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Pt(IV) complexes trans-Pt(PEt3)2(R)(Br)3 (R = Br, aryl and polycyclic aromatic fragments) photoeliminate molecular bromine with quantum yields as high as 82%. Photoelimination occurs both in the solid state and in solution. Calorimetry measurements and DFT calculations (PMe3 analogs) indicate endothermic and endergonic photoeliminations with free energies from 2 to 22 kcal/mol of Br2. Solution trapping experiments with high concentrations of 2,3-dimethyl-2-butene suggest a radical-like excited state precursor to bromine elimination.
- Raphael Karikachery, Alice,Lee, Han Baek,Masjedi, Mehdi,Ross, Andreas,Moody, Morgan A.,Cai, Xiaochen,Chui, Megan,Hoff, Carl D.,Sharp, Paul R.
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supporting information
p. 4113 - 4119
(2013/05/09)
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- Synthesis and spectral properties of ruthenium(II) complexes based on 2,2′-bipyridines modified by a perylene chromophore
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Five new 2,2′-bipyridines functionalized with a perylene or a perylenediimide moiety were synthesized and the corresponding heteroleptic ruthenium(II) complexes ([Ru(bpy)2(L)](PF6)2; bpy = 2,2′-bipyridyl, L = perylene-substituted bpy ligand) were prepared. The UV-vis spectra of the ruthenium(II) complexes showed red-shifted and intense absorption bands derived from the conjugated structure of the new ligands.
- Kodama, Koichi,Kobayashi, Akinori,Hirose, Takuji
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supporting information
p. 5514 - 5517
(2013/09/23)
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- INDENOPERYLENE COMPOUND, MATERIAL FOR ORGANIC THIN-FILM PHOTOVOTAIC CELL CONTAINING INDENOPERYLENE DERIVATIVE, AND ORGANIC THIN-FILM PHOTOVOTAIC CELL USING SAME
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An indenoperylene derivative represented by a formula (A-1), wherein in the formula (A-1), at least one of R1 to R16 is an amino group represented by the formula (A-2). In the formula (A-2), Ra and Rb are a substituted or unsubstituted aryl group having 6 to 40 ring carbon atoms or a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms.
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Paragraph 0097
(2013/06/27)
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- Methylterrylene isomers
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2-Methyl and 3-methylterrylenes have been obtained by Suzuki coupling of 3-bromoperylene and corresponding methylnaphthylboronic acids or esters, giving methylnaphthylperylene isomers, followed by Scholl cyclodehydrogenation; the latter reaction gave also the other cyclodehydrogenation isomers 10- (respectively, 9-) methylbenzo[4,5]indeno[1,2,3-cd]perylene.
- Nagarajan, Samuthira,Barthes, Cecile,Girdhar, Navdeep K.,Dang, Tung T.,Gourdon, Andre
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p. 9371 - 9375,5
(2012/12/12)
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- Substitution effects of C≡C triple bonds on the fluorescent properties of perylenes studied by emission and transient absorption measurements
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Perylenes substituted with trimethylsilylethynyl, tert-butylethynyl and trimethylsilylbutadiynyl groups were prepared, and their photophysical and photochemical properties were investigated through measurements of fluorescence yields, lifetimes, and tripl
- Yamaji, Minoru,Maeda, Hajime,Nanai, Yasuaki,Mizuno, Kazuhiko
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experimental part
p. 72 - 76
(2012/08/07)
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- PHOSPHINE COMPOUND, PROCESS FOR PRODUCING THE SAME, AND PEROXIDE SCAVENGER USING THE SAME
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The invention provides a novel peroxide scavenger comprising a phosphine compound represented by general formula [I]: wherein Z1 and Z2 each represents a cyclic group; Ar represents an arylene group; R represents an aliphatic hydrocarbon group; Y represents phosphorus (P), nitrogen (N), or bismuth (Bi); and R1, R2, and R3 each represents a cyclic group, particularly a peroxide scavenger that can scavenge peroxides such as reactive oxygen species which are generated in mitochondria upon exposure to oxidative stress and localized in mitochondria. The phosphine compound of the invention is oxidized by the peroxides localized in mitochondria to increase the fluorescence intensity, whereby the peroxides can be scavenged.
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Page/Page column 12
(2011/02/18)
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- Synthesis of spiropyrans as building blocks for molecular switches and dyads
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The synthesis of spiropyrans was improved significantly with use of ultrasonic radiation. To show the broad applicability of this methodology a range of spiropyrans were prepared which are equipped with iodo, hydroxyl, ethinyl, or azido groups as potential building blocks for conjugation to functional ?-systems or biopolymers. Representatively, the conjugation chemistry was demonstrated for the preparation of spiropyran conjugates with pyrene, perylene, and nile red via the lick-type cycloaddition. These molecular dyads were characterized by optical spectroscopy.
- Beyer, Christoph,Wagenknecht, Hans-Achim
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supporting information; experimental part
p. 2752 - 2755
(2010/07/09)
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- Highly fluorescent platinum(II) organometallic complexes of perylene and perylene monoimide, with Pt σ-bonded directly to the perylene core
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3-Bromoperylene (BrPer) or N-(2,5-di-tert-butylphenyl)-9-bromo-perylene-3, 4-dicarboximide (BrPMI) react with [Pt(PEt3)4] to yield trans-[PtR(PEt3)2Br] (R = Per, 1a; R = PMI, 1b). Neutral and cationic perylenyl complexes containing a Pt(PEt3)X group have been prepared from 1a,b by substitution of the Br ligand by a variety of other ligands (NCS, CN, NO3, CNtBu, PyMe). The X-ray structures of trans-[PtR(PEt3)2X] (R =Per, X = NCS (2a);R =PMI, X= NO3 (4b); R = Per, X = CNtBu (5a)) show that the perylenyl fragment remains nearly planar and is arranged almost orthogonal to the coordination plane: The three molecules appear as individual entities in the solid state, with no π-π stacking of perylenyl rings. Each platinum complex exhibits fluorescence associated to the perylene or PMI fragments with emission quantum yields, in solution at room temperature, in the range 0.30-0.80 and emission lifetimes ~4 ns, but with significantly different emission maxima, by influence of the X ligands on Pt. The similarity of the overall luminescence spectra of these metalated complexes with the perylene or PMI strongly suggests a perylene-dominated intraligand π- π*emissive state, metal-perturbed by interaction of the platinum fragment mostly via polarization of the Ar-Pt bond.
- Lentijo, Sergio,Miguel, Jesus A.,Espinet, Pablo
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body text
p. 9169 - 9177
(2011/01/12)
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- Electrophilic substitution of two monohomoperylenes and perylene
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Various types of electrophilic substitution of monohomoperylene (1) and its 11,11-difluoro derivative (2) have been studied, viz, bromination, nitration, acylation, formylation and sulfonation.Bromination with N-bromosuccinimide (NBS) of 1 in dichloromethane leads to initial substitution mainly at the α position 2 and 10, i.e., of the annuleno moiety, followed by further substitution of the β positions 4 and 8 of the same moiety, and of the α positions 2' and 10' of the naphthaleno moiety.Reaction of 1 with 5.0 mol-equiv. of NBS yields 2,4,8,10,2'-pentabromo-1 in 46percent yield.Sulfonation of 1 with SO3 in dichloromethane using 1.2 mol-equiv. of dioxane as reactivity moderator leads to the formation of 1-2-sulfonic acid (1-2-S), 1-2,10-S2, and the intermediate ? complex 6.Sulfonation of the 11,11-difluoro derivative 2 leads to the formation of 2-2-S, 2-2,10-S2 and 2-2,10-disulfonic anhydride (7), together with small amounts of 2-2,2'-S2 or/and 2-2,10'-S2.The other types of electrophilic substitution of 1 and 2 studied were found to proceed similarly, in that the initial substitution occurs at the 2-position and the subsequent one at the 10-position, i.e., peri to the primarily introduced substituent.The chemical behaviour (i.e., the substitution pattern and relative reactivity) of the two monohomoperylenes 1 and 2 have been compared with that of 1,6-methanoannulene (3), its 11,11-difluoro derivative (4), and perylene (5).For example, the sulfonation reactivity ratio of the naphthalene to the annuleno moiety is significantly greater for 2 than 1, as predicted on the basis of the higher sulfonation reactivity of 3 compared to 4.
- Cerfontain, Hans,Koeberg-Telder, Ankie,Lerch, Ulrike
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p. 584 - 594
(2007/10/02)
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- Methylterrylene isomers
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2-Methyl and 3-methylterrylenes have been obtained by Suzuki coupling of 3-bromoperylene and corresponding methylnaphthylboronic acids or esters, giving methylnaphthylperylene isomers, followed by Scholl cyclodehydrogenation; the latter reaction gave also the other cyclodehydrogenation isomers 10- (respectively, 9-) methylbenzo[4,5]indeno[1,2,3-cd]perylene.
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