- Flash vacuum thermolysis of acenaphtho[1,2-a]acenaphthylene, fluoranthene, benzo[k]- and benzo[j]fluoranthene - Homolytic scission of carbon-carbon single bonds of internally fused cyclopenta moieties at T ≥ 1100°C
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Flash vacuum thermolysis (FVT, 1000 °C ≥ T ≥ 1200 °C) of acenaphtho[1,2-a]acenaphthylene (3, C22H12) gave the C22H12 cyclopenta-fused polycyclic aromatic hydrocarbon (CP-PAH) acenaphtho[1,2- e]acenaphthylene (4), cyclopenta[cd]perylene (5) and cyclopenta[def]benzo[hi]chrysene (6). Whereas the formation of 4 is explained by a ring contraction/ring expansion rearrangement of 3, the identification of 5 and 6 suggests that 3 also undergoes homolytic scission of a five- membered ring's carbon-carbon single bond furnishing the transient diradical intermediate 7. Ring closure of 7 to form 8 after rotation around the carbon- carbon single bond of the intact five-membered ring followed by hydrogen shifts will give 6. The latter can rearrange subsequently into 5 by ring contraction/ring expansion. The structural assignment of 4 and 5 was supported by independent FVT of 6,12-bis(1-chloroethenyl)chrysene (14) and 3- (1-chloroethenyl)perylene (23), respectively. FVT of 14 (900-1200 °C) gave in a consecutive process 6,12-bis(ethynyl)chrysene (15), 9- ethynylbenz[j]acephenanthrylene (16) and bis(cyclopenta[hi,qr])chrysene (17). Although at T ≥ 900 °C 17 selectively rearranges into 4 by ring contraction/ring expansion, at 1200 °C the latter is converted into 5 presumably via a diradical intermediate obtained by homolytic scission of a single carbon-carbon bond of a five-membered ring. FVT of 23 gave in situ 3- ethynylperylene (25), which at 1000 °C is nearly quantitatively converted into 5. The propensity of internal cyclopenta moieties to undergo homolytic scission of a five-membered ring's carbon-carbon single bond was corroborated by independent FVT of benzo[k]- (11) and benzo[j]fluoranthene (12). Previously unknown thermal pathways to important (CP)-PAH combustion effluents are disclosed at T≥ 1000 °C.
- Sarobe, Martin,Kwint, Huibert C.,Fleer, Theun,Havenith, Remco W.A.,Jenneskens, Leonardas W.,Vlietstra, Edward J.,Van Lenthe, Joop H.,Wesseling, Jolanda
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- From chrysene to double [5] Helicenes
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Glyoxylic functionalization of chrysene by Friedel-Crafts acylation with ethyl chloroglyoxylate or by bromination followed by substituent exchange enables the formation of bis[5]helicene-tetracarboxylates and tetracarboxdiimides through Perkin reactions and palladium-catalyzed cyclizations. Tetrasubstituted bishelicenic dichrysenoanthracenes and dinaphthochrysenes are thus obtained from chrysene in four to six steps. In the cyclization to dinaphthochrysenes, a rearrangement of the conjugated carbon skeleton is identified as side reaction. In solution, the diimides form mixtures of M,P- and M,M/P,P-diastereomers, which equilibrate at room temperature when the helices are distant but equilibrate only upon heating when the helices are close and acting in concert. The nonplanar arene geometry allows close π-contacts in two dimensions between neighboring molecules in the crystal.
- Bock, Harald,Huet, Stephanie,Dechambenoit, Pierre,Hillard, Elizabeth A.,Durola, Fabien
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Read Online
- AROMATIC AMINE DERIVATIVE AND ORGANIC ELECTROLUMINESCENT DEVICES CONTAINING THE SAME
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To further develop a fluorescent light emitting material so as to obtain a higher element efficiency, a longer lifetime of the device, and more blue emission.SOLUTION: The invention discloses aromatic amine derivative, and an organic electroluminescent device including the same. In a structure, fluorene/silafluorene groups with ortho-substituents are introduced into the aromatic amine derivative, therefore the aromatic amine derivative can be used as light-emitting materials in a light-emitting layer of the organic electroluminescent device. These novel compounds can provide better device performance.SELECTED DRAWING: None
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Paragraph 0112-0113
(2021/03/03)
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- Chrysene-Based Azahelicene π-Linker of D-π-D-Type Hole-Transporting Materials for Perovskite Solar Cells
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Chrysene is a readily available material for exploring new polycyclic aromatic hydrocarbons (PAHs). In this study, two chrysene based azahelicenes, nine-membered BA7 and ten-membered DA6, are constructed by intermolecular oxidative annulation of 6-aminochrysene and intramolecular annulation of N6,N12-bis(1-chloronaphthalen-2-yl)chrysene-6,12-diamine, respectively. The hexylated BA7 and DA6 and their brominated products were undoubtedly characterized by single crystal XRD. Subsequent amination with bis(9-methyl-9H-carbazol-3-yl)amine (BMCA) electron donor afforded D-π-D-type semiconductors BA7-BMCA and DA6-BMCA with beneficial properties to act as hole transport materials for perovskite solar cell. Compared with 19.4 % champion power conversion efficiency (PCE) of BA7-BMCA based device, a higher PCE of 20.2 % for DA6-BMCA counterpart may be attributed to its S-shaped double helicene-like linker with extended π-conjugated system.
- Tang, Zefeng,Li, Tianyu,Cao, Yucai,Zhang, Yuyan,He, Lifei,Zheng, Aibin,Lei, Ming
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p. 4923 - 4928
(2021/10/19)
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- Regioselective arene homologation through rhenium-catalyzed deoxygenative aromatization of 7-oxabicyclo[2.2.1]hepta-2,5-dienes
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Combined use of oxorhenium catalysts with triphenyl phosphite as an oxygen acceptor allowed efficient deoxygenative aromatization of oxabicyclic dienes. The reaction proceeded under neutral conditions and was compatible with various functional groups. Combining this deoxygenation with regioselective bromination and trapping of the generated aryne with furan resulted in benzannulative π-extension at the periphery of the PAHs. This enabled direct use of unfunctionalized PAHs for extension of π-conjugation. Iteration of the transformations increased the number of fused-benzene rings one at a time, which has the potential to alter the properties of PAHs by fine-tuning the degree of π-conjugation, shape, and edge topology.
- Murai, Masahito,Ogita, Takuya,Takai, Kazuhiko
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supporting information
p. 2332 - 2335
(2019/02/27)
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- Observation of the rare chrysene excimer
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Formation of the so far elusive chrysene excimer in solution is achieved by using DNA as a supramolecular scaffold. Oligonucleotides possessing one or two chrysene building blocks have been synthesized. Chrysene excimer fluorescence has been unambiguously observed in DNA double strands, as well as in single strands containing two neighbouring chrysenes.
- Khorev, Oleg,Boesch, Caroline D.,Probst, Markus,Haener, Robert
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p. 1506 - 1512
(2014/03/21)
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- COMPOUND HAVING SPIRO BOND, MATERIAL FOR LUMINESCENT COATING FORMATION AND ORGANIC ELECTROLUMINESCENCE ELEMENT INCLUDING THE SAME
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A novel compound having a spiro bond with a specific structure, a material for forming a luminous coated film comprising the compound having the spiro bond with the specific structure, and an organic electroluminescence device which comprises at least one organic thin film layer sandwiched between a pair of electrode consisting of an anode and a cathode, wherein the organic thin film layer comprises the compound having the spiro bond. The organic EL device employing either the compound having a spiro bond or the material for forming luminous coated film in accordance with the present invention is superior in heat resistance, has stability of the thin film composing the device, emits uniform blue light, and exhibits an excellent luminance, current efficiency even under a low driving voltage.
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Page/Page column 36
(2010/11/08)
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