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Noboru Morita - One of the best experts on this subject based on the ideXlab platform.
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synthesis of novel thiophene fused 1 1 biAzulene derivative by the reaction of azuleno 1 2 b thiophene with n iodosuccinimide
Heterocycles, 2013Co-Authors: Taku Shoji, Shunji Ito, Masafumi Yasunami, Yuta Inoue, Erika Shimomura, Mitsuhisa Maruyama, Atsuyo Yamamoto, Kunihide Fujimori, Noboru MoritaAbstract:Novel thiophene-fused 1,1’-biAzulene derivative was prepared by the reaction of azuleno[1,2-b]thiophene with N-iodosuccinimide. The electronic properties of the new 1,1’-biAzulene derivative obtained by the reaction were characterized by CV, DPV, and UV/Vis spectroscopy. N-Iodosuccinimide (NIS) is one of the efficient reagents for the iodation of organic compound. Thus, in the Azulene chemistry, several 1-iodoAzulene derivatives have been prepared by the reaction with NIS. Recently, Abe et al. have reported the generation of 1,1’-biAzulene and 1,1’:6’,1”-terAzulene derivatives by the reaction of ethyl 2-aminoAzulene-1-carboxylate with NIS. They proposed a radical mechanism for the oxidative-coupling reaction quoted our previous reports. Several synthetic methodologies of 1,1'-biAzulenes have been reported in the literatures. However, in most cases the methodologies require metal catalyst, high temperature reaction, and/or longer reaction period. Thus, the reaction reported by Abe et al. could become one of the innovative synthetic methodologies from the viewpoint of metal-free synthesis of 1,1’-biAzulene derivatives. Azulene-fused heterocycles have attracted the interest owing to its unusual chemical properties. Thus, preparation and reactivities of a number of Azulene-fused heterocycles have already been revealed by many research groups. However, 1,1’-biAzulene derivatives HETEROCYCLES, Vol. 87, No. 2, 2013 303
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synthesis of 2 azulenyl 1 1 4 4 tetracyano 3 ferrocenyl 1 3 butadienes by 2 2 cycloaddition of ferrocenylethynyl Azulenes with tetracyanoethylene
Chemistry: A European Journal, 2013Co-Authors: Taku Shoji, Tetsuo Okujima, Noboru MoritaAbstract:1-, 2-, and 6-(Ferrocenylethynyl)Azulene derivatives 10–16 have been prepared by palladium-catalyzed alkynylation of ethynylferrocene with the corresponding haloAzulenes under Sonogashira–Hagihara conditions. Compounds 10–16 reacted with tetracyanoethylene (TCNE) in a [2+2] cycloaddition–cycloreversion reaction to afford the corresponding 2-azulenyl-1,1,4,4,-tetracyano-3-ferrocenyl-1,3-butadiene chromophores 17–23 in excellent yields. The redox behavior of the novel Azulene chromophores 17–23 was examined by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.
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first synthesis of 2 heteroarylAzulenes by the electrophilic substitution of Azulene with triflate of n containing heterocycles
Heterocycles, 2012Co-Authors: Taku Shoji, Tetsuo Okujima, Shunji Ito, Yuta Inoue, Noboru MoritaAbstract:An efficient synthesis of 2-heteroarylAzulene derivatives was established via electrophilic substitution. The reaction of 6-dimethylamino-1,3-di(methylthio)Azulene (1a) with the triflate of N-containing heteroarenes proceeded in the presence of excess heteroarenes to afford the corresponding 2-dihydroheteroarylAzulene derivatives 3−7. The 2-dihydroheteroarylAzulene derivatives were readily converted into the desired 2-heteroarylAzulene derivatives 8−11 by the treatment with KOH in alcohols in excellent yields, except for 4 and 5. Electrophilic substitution reactions are a very important and general methodology for the functionalization of aromatic compounds. In Azulene derivatives, there are numerous reports for the electrophilic substitution reactions at the 1and 3-positions of the Azulene ring. However, there are few reports on the functionalization of Azulene derivatives at the 2-position utilizing electrophilic substitution reactions, because 2-position of Azulene is inert site toward the electrophile. In 1962, Hafner and co-workers reported that 1,3-dialkyl-substituted Azulene derivatives undergo the Vilsmeier formylation reaction using DMF and POCl3 to give corresponding 2-formylAzulenes, but only with very low selectivity compared to ipso-substitution at the 1-position and electrophilic substitution at the 5-position. HETEROCYCLES, Vol. 85, No. 1, 2012 35
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synthesis of push pull chromophores by the sequential 2 2 cycloaddition of 1 azulenylbutadiynes with tetracyanoethylene and tetrathiafulvalene
Organic and Biomolecular Chemistry, 2012Co-Authors: Taku Shoji, Tetsuo Okujima, Noboru MoritaAbstract:Azulene-substituted butadiynes have been prepared by Cu-mediated cross- and homo-coupling reactions. The Azulene-substituted butadiynes reacted with tetracyanoethylene in a formal [2 + 2] cycloaddition reaction to afford the corresponding 1,1,4,4-tetracyanobutadiene chromophores, in excellent yields. Further [2 + 2] cycloaddition with TTF and TCNE gave novel donor–acceptor chromophores and novel Azulene-substituted 6,6-dicyanofulvene derivatives.
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synthesis of push pull chromophores by the sequential 2 2 cycloaddition of 1 azulenylbutadiynes with tetracyanoethylene and tetrathiafulvalene
Organic and Biomolecular Chemistry, 2012Co-Authors: Taku Shoji, Tetsuo Okujima, Noboru MoritaAbstract:Azulene-substituted butadiynes have been prepared by Cu-mediated cross- and homo-coupling reactions. The Azulene-substituted butadiynes reacted with tetracyanoethylene in a formal [2 + 2] cycloaddition reaction to afford the corresponding 1,1,4,4-tetracyanobutadiene chromophores, in excellent yields. Further [2 + 2] cycloaddition with TTF and TCNE gave novel donor–acceptor chromophores and novel Azulene-substituted 6,6-dicyanofulvene derivatives.
Taku Shoji - One of the best experts on this subject based on the ideXlab platform.
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synthesis of novel thiophene fused 1 1 biAzulene derivative by the reaction of azuleno 1 2 b thiophene with n iodosuccinimide
Heterocycles, 2013Co-Authors: Taku Shoji, Shunji Ito, Masafumi Yasunami, Yuta Inoue, Erika Shimomura, Mitsuhisa Maruyama, Atsuyo Yamamoto, Kunihide Fujimori, Noboru MoritaAbstract:Novel thiophene-fused 1,1’-biAzulene derivative was prepared by the reaction of azuleno[1,2-b]thiophene with N-iodosuccinimide. The electronic properties of the new 1,1’-biAzulene derivative obtained by the reaction were characterized by CV, DPV, and UV/Vis spectroscopy. N-Iodosuccinimide (NIS) is one of the efficient reagents for the iodation of organic compound. Thus, in the Azulene chemistry, several 1-iodoAzulene derivatives have been prepared by the reaction with NIS. Recently, Abe et al. have reported the generation of 1,1’-biAzulene and 1,1’:6’,1”-terAzulene derivatives by the reaction of ethyl 2-aminoAzulene-1-carboxylate with NIS. They proposed a radical mechanism for the oxidative-coupling reaction quoted our previous reports. Several synthetic methodologies of 1,1'-biAzulenes have been reported in the literatures. However, in most cases the methodologies require metal catalyst, high temperature reaction, and/or longer reaction period. Thus, the reaction reported by Abe et al. could become one of the innovative synthetic methodologies from the viewpoint of metal-free synthesis of 1,1’-biAzulene derivatives. Azulene-fused heterocycles have attracted the interest owing to its unusual chemical properties. Thus, preparation and reactivities of a number of Azulene-fused heterocycles have already been revealed by many research groups. However, 1,1’-biAzulene derivatives HETEROCYCLES, Vol. 87, No. 2, 2013 303
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synthesis of 2 azulenyl 1 1 4 4 tetracyano 3 ferrocenyl 1 3 butadienes by 2 2 cycloaddition of ferrocenylethynyl Azulenes with tetracyanoethylene
Chemistry: A European Journal, 2013Co-Authors: Taku Shoji, Tetsuo Okujima, Noboru MoritaAbstract:1-, 2-, and 6-(Ferrocenylethynyl)Azulene derivatives 10–16 have been prepared by palladium-catalyzed alkynylation of ethynylferrocene with the corresponding haloAzulenes under Sonogashira–Hagihara conditions. Compounds 10–16 reacted with tetracyanoethylene (TCNE) in a [2+2] cycloaddition–cycloreversion reaction to afford the corresponding 2-azulenyl-1,1,4,4,-tetracyano-3-ferrocenyl-1,3-butadiene chromophores 17–23 in excellent yields. The redox behavior of the novel Azulene chromophores 17–23 was examined by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.
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first synthesis of 2 heteroarylAzulenes by the electrophilic substitution of Azulene with triflate of n containing heterocycles
Heterocycles, 2012Co-Authors: Taku Shoji, Tetsuo Okujima, Shunji Ito, Yuta Inoue, Noboru MoritaAbstract:An efficient synthesis of 2-heteroarylAzulene derivatives was established via electrophilic substitution. The reaction of 6-dimethylamino-1,3-di(methylthio)Azulene (1a) with the triflate of N-containing heteroarenes proceeded in the presence of excess heteroarenes to afford the corresponding 2-dihydroheteroarylAzulene derivatives 3−7. The 2-dihydroheteroarylAzulene derivatives were readily converted into the desired 2-heteroarylAzulene derivatives 8−11 by the treatment with KOH in alcohols in excellent yields, except for 4 and 5. Electrophilic substitution reactions are a very important and general methodology for the functionalization of aromatic compounds. In Azulene derivatives, there are numerous reports for the electrophilic substitution reactions at the 1and 3-positions of the Azulene ring. However, there are few reports on the functionalization of Azulene derivatives at the 2-position utilizing electrophilic substitution reactions, because 2-position of Azulene is inert site toward the electrophile. In 1962, Hafner and co-workers reported that 1,3-dialkyl-substituted Azulene derivatives undergo the Vilsmeier formylation reaction using DMF and POCl3 to give corresponding 2-formylAzulenes, but only with very low selectivity compared to ipso-substitution at the 1-position and electrophilic substitution at the 5-position. HETEROCYCLES, Vol. 85, No. 1, 2012 35
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synthesis of push pull chromophores by the sequential 2 2 cycloaddition of 1 azulenylbutadiynes with tetracyanoethylene and tetrathiafulvalene
Organic and Biomolecular Chemistry, 2012Co-Authors: Taku Shoji, Tetsuo Okujima, Noboru MoritaAbstract:Azulene-substituted butadiynes have been prepared by Cu-mediated cross- and homo-coupling reactions. The Azulene-substituted butadiynes reacted with tetracyanoethylene in a formal [2 + 2] cycloaddition reaction to afford the corresponding 1,1,4,4-tetracyanobutadiene chromophores, in excellent yields. Further [2 + 2] cycloaddition with TTF and TCNE gave novel donor–acceptor chromophores and novel Azulene-substituted 6,6-dicyanofulvene derivatives.
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synthesis of push pull chromophores by the sequential 2 2 cycloaddition of 1 azulenylbutadiynes with tetracyanoethylene and tetrathiafulvalene
Organic and Biomolecular Chemistry, 2012Co-Authors: Taku Shoji, Tetsuo Okujima, Noboru MoritaAbstract:Azulene-substituted butadiynes have been prepared by Cu-mediated cross- and homo-coupling reactions. The Azulene-substituted butadiynes reacted with tetracyanoethylene in a formal [2 + 2] cycloaddition reaction to afford the corresponding 1,1,4,4-tetracyanobutadiene chromophores, in excellent yields. Further [2 + 2] cycloaddition with TTF and TCNE gave novel donor–acceptor chromophores and novel Azulene-substituted 6,6-dicyanofulvene derivatives.
Masahito Murai - One of the best experts on this subject based on the ideXlab platform.
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Azulene fused linear polycyclic aromatic hydrocarbons with small bandgap high stability and reversible stimuli responsiveness
Organic Letters, 2017Co-Authors: Masahito Murai, Shinji Iba, Hiromi Ota, Kazuhiko TakaiAbstract:Azulene-fused polycyclic aromatic hydrocarbons (PAHs) were synthesized from commercially available Azulene in four steps. The resulting Azulene conjugates exhibited significantly narrow HOMO–LUMO bandgaps with high air stability, confirmed by photophysical study. Introduction of Azulene also enabled the unique reversible stimuli-responsiveness even with the weak acid and base, which can potentially control the degree of conjugation and optoelectronic properties by simple acid–base and redox processes.
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palladium catalyzed direct arylation of Azulene based on regioselective c h bond activation
ChemInform, 2016Co-Authors: Masahito Murai, Mayu Yanagawa, Masahiro Nakamura, Kazuhiko TakaiAbstract:An efficient synthesis of arylAzulenes involving minimal steps was developed. The combination of Pd(OAc)2/XPhos as a catalyst and pivalic acid as an additive was key for the direct arylation of C−H bonds, and the reaction proceeded preferentially at the 1- and 3-positions of Azulene, without heteroatom-containing directing groups. Compared with the traditional cross-coupling protocol, the arylation method described here requires fewer steps and uses commercially available synthetic blocks. The degree of conjugation and the optical properties of the resulting Azulene conjugates can be adjusted by simple protonation, which allows the current method to be an efficient strategy for exploiting novel Azulene-based functional materials.
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iridium catalyzed dehydrogenative silylation of Azulenes based on regioselective c h bond activation
ChemInform, 2015Co-Authors: Masahito Murai, Keishi Takami, Hirotaka Takeshima, Kazuhiko TakaiAbstract:The silylation of Azulene with various hydrosilanes proceeds with excellent regioselectivity to form 2-silylAzulenes without the need for any directing groups.
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iridium catalyzed dehydrogenative silylation of Azulenes based on regioselective c h bond activation
Organic Letters, 2015Co-Authors: Masahito Murai, Keishi Takami, Hirotaka Takeshima, Kazuhiko TakaiAbstract:Use of an iridium catalyst allowed the efficient dehydrogenative functionalization of C–H bonds of Azulenes with the production of hydrogen as the sole byproduct. The reaction occurred with excellent chemo- and regioselectivities to provide 2-silylAzulenes even without any directing groups. Effective conjugation through the 2-position of the Azulene ring was demonstrated by the unique stimuli-responsiveness against an acid–base reaction.
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modulating the properties of Azulene containing polymers through controlled incorporation of regioisomers
Advanced Functional Materials, 2014Co-Authors: Kazuhiko Tsurui, Masahito Murai, Craig J Hawker, Maxwell J RobbAbstract:Two libraries of random conjugated polymers are presented that incorporate varying ratios of regioisomeric Azulene units connected via the 5-membered or 7-membered ring in combination with bithiophene or fluorene comonomers. It is demonstrated that the optoelectronic and stimuli-responsive properties of the materials can be systematically modulated by tuning the relative percentage of each Azulene building block in the polymer backbone. Significantly, these materials exhibit stimuli-responsive behavior in the solid state with spin-coated thin films undergoing rapid and reversible color switching. Ultimately, this work introduces a new design strategy in which the optoelectronic properties of conjugated polymers can be modulated by varying only the regiochemistry of the constituent building blocks along a polymer chain.
Shunji Ito - One of the best experts on this subject based on the ideXlab platform.
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synthesis of novel thiophene fused 1 1 biAzulene derivative by the reaction of azuleno 1 2 b thiophene with n iodosuccinimide
Heterocycles, 2013Co-Authors: Taku Shoji, Shunji Ito, Masafumi Yasunami, Yuta Inoue, Erika Shimomura, Mitsuhisa Maruyama, Atsuyo Yamamoto, Kunihide Fujimori, Noboru MoritaAbstract:Novel thiophene-fused 1,1’-biAzulene derivative was prepared by the reaction of azuleno[1,2-b]thiophene with N-iodosuccinimide. The electronic properties of the new 1,1’-biAzulene derivative obtained by the reaction were characterized by CV, DPV, and UV/Vis spectroscopy. N-Iodosuccinimide (NIS) is one of the efficient reagents for the iodation of organic compound. Thus, in the Azulene chemistry, several 1-iodoAzulene derivatives have been prepared by the reaction with NIS. Recently, Abe et al. have reported the generation of 1,1’-biAzulene and 1,1’:6’,1”-terAzulene derivatives by the reaction of ethyl 2-aminoAzulene-1-carboxylate with NIS. They proposed a radical mechanism for the oxidative-coupling reaction quoted our previous reports. Several synthetic methodologies of 1,1'-biAzulenes have been reported in the literatures. However, in most cases the methodologies require metal catalyst, high temperature reaction, and/or longer reaction period. Thus, the reaction reported by Abe et al. could become one of the innovative synthetic methodologies from the viewpoint of metal-free synthesis of 1,1’-biAzulene derivatives. Azulene-fused heterocycles have attracted the interest owing to its unusual chemical properties. Thus, preparation and reactivities of a number of Azulene-fused heterocycles have already been revealed by many research groups. However, 1,1’-biAzulene derivatives HETEROCYCLES, Vol. 87, No. 2, 2013 303
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first synthesis of 2 heteroarylAzulenes by the electrophilic substitution of Azulene with triflate of n containing heterocycles
Heterocycles, 2012Co-Authors: Taku Shoji, Tetsuo Okujima, Shunji Ito, Yuta Inoue, Noboru MoritaAbstract:An efficient synthesis of 2-heteroarylAzulene derivatives was established via electrophilic substitution. The reaction of 6-dimethylamino-1,3-di(methylthio)Azulene (1a) with the triflate of N-containing heteroarenes proceeded in the presence of excess heteroarenes to afford the corresponding 2-dihydroheteroarylAzulene derivatives 3−7. The 2-dihydroheteroarylAzulene derivatives were readily converted into the desired 2-heteroarylAzulene derivatives 8−11 by the treatment with KOH in alcohols in excellent yields, except for 4 and 5. Electrophilic substitution reactions are a very important and general methodology for the functionalization of aromatic compounds. In Azulene derivatives, there are numerous reports for the electrophilic substitution reactions at the 1and 3-positions of the Azulene ring. However, there are few reports on the functionalization of Azulene derivatives at the 2-position utilizing electrophilic substitution reactions, because 2-position of Azulene is inert site toward the electrophile. In 1962, Hafner and co-workers reported that 1,3-dialkyl-substituted Azulene derivatives undergo the Vilsmeier formylation reaction using DMF and POCl3 to give corresponding 2-formylAzulenes, but only with very low selectivity compared to ipso-substitution at the 1-position and electrophilic substitution at the 5-position. HETEROCYCLES, Vol. 85, No. 1, 2012 35
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first synthesis of 1 indol 2 yl Azulenes by the vilsmeier haack type arylation with triflic anhydride as an activating reagent
Tetrahedron Letters, 2012Co-Authors: Taku Shoji, Yuta Inoue, Shunji ItoAbstract:Abstract Azulene derivatives reacted with 2-indolinones in the presence of triflic anhydride (Tf 2 O) to afford 1-(indol-2-yl)Azulenes in good yields. In the cases of the reaction of 6- tert -butyl-1-(methylthio)Azulene ( 11 ) and 1-(1,4-dihydropyridin-4-yl)Azulene 14 , 1,1′-biAzulene derivative 24 and 1-(indol-2-yl)Azulene ( 2 ) were obtained under the similar reaction conditions, respectively, instead of the presumed electrophilic substitution products.
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reactions between 1 ethynylAzulenes and 7 7 8 8 tetracyanoquinodimethane tcnq preparation properties and redox behavior of novel Azulene substituted redox active chromophores
European Journal of Organic Chemistry, 2009Co-Authors: Taku Shoji, Shunji Ito, Kozo Toyota, Masafumi Yasunami, Takeaki Iwamoto, Noboru MoritaAbstract:[2+2] Cycloaddition/cycloreversion reactions between TCNQ and mono- or bis[2-(azulen-1-yl)ethynyl]benzene or -thiophene derivatives were examined: the corresponding TCNQ adducts, novel Azulene-substituted redox-active chromophores, were produced in excellent yields. TCNE/TCNQ double adducts were also prepared both by stepwise and by one-pot cascade reactions. The redox behavior of these novel Azulene-substituted chromophores was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Significant color changes in these Azulene-substituted chromophores under electrochemical reduction conditions were observed by visible spectroscopy. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
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heteroarylation of 1 azulenyl methyl sulfide two step synthetic strategy for 1 methylthio 3 heteroaryl Azulenes using the triflate of n containing heterocycles
European Journal of Organic Chemistry, 2008Co-Authors: Junya Higashi, Taku Shoji, Shunji Ito, Kozo Toyota, Masafumi Yasunami, Noboru MoritaAbstract:1-Azulenyl methyl sulfide reacts with highly electrophilic trifluoromethanesulfonates of N-heterocycles, that is, pyridine, isoquinoline, 1,10-phenanthroline, benzothiazole, quinoline, and acridine, to give 1-methylthio-3-(dihydroheteroaryl)Azulenes in good yields. In the case of the reaction with the trifluoromethanesulfonate of pyridine, 1-methylthio-3-pyridylAzulene was obtained directly under certain reaction conditions. Treatment of the 1-methylthio-3-(dihydroheteroaryl)Azulenes with KOH or tBuOK afforded the corresponding 1-methylthio-3-(heteroaryl)Azulenes in good yields. The redox behavior of these 1-methylthio-3-(heteroaryl)Azulenes was examined by cyclic voltammetry and differential pulse voltammetry.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Xike Gao - One of the best experts on this subject based on the ideXlab platform.
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Azulene based π functional materials design synthesis and applications
Accounts of Chemical Research, 2021Co-Authors: Hanshen Xin, Bin Hou, Xike GaoAbstract:ConspectusAzulene, an isomer of naphthalene, is a molecule of historical interest for its unusual photophysical properties, including a beautiful blue color derived from the narrow HOMO-LUMO energy gap and anti-Kasha fluorescence from S2 to S0. More recently, it has attracted increasing attention for its novel electronic structure, including an electron-rich five-membered ring and an electron-deficient seven-membered ring with a dipole moment of 1.08 D resulting from resonance delocalization, its different reactivities at odd and even positions, and its stimuli-responsive behavior. As a key building block, Azulene has been used in various fields because of its unique physicochemical properties. Recent studies have demonstrated the great potential of Azulene for constructing advanced organic materials. However, exploring Azulene-based materials has long been hindered by challenges in molecular design and synthesis. Most of the reported Azulene-based materials have the Azulene unit incorporated through the five-membered ring or seven-membered ring. Creating Azulene-based novel building blocks for optoelectronics and using 2,6-connected Azulene units to construct conjugated polymers that can adequately utilize the "donor-acceptor" structure of Azulene remained underexplored before our contributions. Besides, for most Azulene-fused polycyclic aromatic hydrocarbons (PAHs) and heteroaromatics, the Azulene substructures were created during later synthesis stages, and the use of Azulene derivatives as starting materials to design and synthesize PAHs and heteroaromatics intelligently is still limited.In this Account, we summarize our efforts on the design, synthesis, and applications of Azulene-based π-functional materials. Our studies start with the creation of novel π-conjugated structures based on Azulene. The design strategy, synthesis, and optoelectronic performance of the first class of Azulene-based aromatic diimides, 2,2'-biAzulene-1,1',3,3'-tetracarboxylic diimide (BAzDI) and its π-extended and π-bridged derivatives, are presented. Notably, antiparallel stacking between adjacent Azulene units derived from Azulene's dipole was observed in single crystals of BAzDI and its derivatives. Besides, we developed an Azulene-fused isoindigo analogue, azulenoisoindigo, which combines the merits of both isoindigo and Azulene, including reversible redox behavior and reversible proton responsiveness. Then we discuss our contributions to the design and synthesis of 2,6-Azulene-based conjugated polymers. By incorporation of 2,6-connected Azulene units into the polymeric backbone, two conjugated polymers with high organic field-effect transistor (OFET) performance were developed. Two 2,6-Azulene-based polymers with proton responsiveness and high electrical conductivity upon protonation were also provided. We also discuss our recent studies on Azulene-based heteroaromatics. Two Azulene-fused BN-heteroaromatics were designed and synthesized, and they exhibited a selective response to fluoride ion and unexpected deboronization upon the addition of trifluoroacetic acid. An unexpected synthesis of Azulene-pyridine-fused heteroaromatics (Az-Py) by reductive cyclization of 1-nitroAzulenes and the OFET performance of Az-Py-1 are included. Afterward, we discuss several examples of Azulene-capped organic conjugated molecules. The molecules capped with the five-membered ring of Azulene favor hole transport, whereas the ones capped with the seven-membered ring favor electron transport.
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Azulene pyridine fused heteroaromatics
Journal of the American Chemical Society, 2020Co-Authors: Hanshen Xin, Xike Gao, Timothy M SwagerAbstract:Azulene, a nonbenzenoid bicyclic aromatic hydrocarbon with unique electronic structure, is a promising building block for constructing nonbenzenoid π-conjugated systems. However, Azulene-fused (hetero)aromatics remain rare as a result of limited synthetic methods. We report herein the unexpected synthesis of Azulene- and pyridine-fused heteroaromatics Az-Py-1, a seven fused ring system with 30π electrons, by reductive cyclization of a 1-nitroAzulene. The structure of Az-Py-1 was unambiguously confirmed by single-crystal X-ray analysis, and analogues Az-Py-2-Az-Py-6 were also synthesized, demonstrating that this is an effective method for constructing Azulene- and pyridine-fused heteroaromatics. Theoretical calculations and photophysical and electrochemical studies of Az-Py-1-Az-Py-6 suggest their potential as semiconductors, and the single-crystal ribbons of Az-Py-1 show high hole mobilities up to 0.29 cm2 V-1 s-1.
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Azulene based bn heteroaromatics
Journal of Organic Chemistry, 2020Co-Authors: Hanshen Xin, Xiaodi Yang, Xike GaoAbstract:Azulene, a nonalternant bicyclic aromatic hydrocarbon, has unique chemical and physical properties and is considered to be a promising building block for constructing novel polycyclic aromatic hydrocarbons (PAHs) and heteroaromatics. We present here the first two Azulene-based BN-heteroaromatics Az-BN-1 and Az-BN-2. The chemical structures and optical and electrochemical properties of both compounds have been investigated, as well as their sensing behavior in response to fluoride ion. Az-BN-1 and Az-BN-2 show different photophysical properties from other reported BN-embedded PAHs, such as lower band gaps and unusual fluorescence. In addition, Az-BN-1 and Az-BN-2 exhibit unexpected deboronization upon addition of trifluoroacetic acid, which distinguishes them from other reported BN-heteroaromatics and can be ascribed to the unique property of the Azulene unit.
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incorporation of 2 6 connected Azulene units into the backbone of conjugated polymers towards high performance organic optoelectronic materials
Angewandte Chemie, 2018Co-Authors: Hanshen Xin, Xuechen Jiao, Xiaodi Yang, Kira Rundel, Christopher R Mcneill, Xike GaoAbstract:Azulene is a promising candidate for constructing optoelectronic materials. An effective strategy is presented to obtain high-performance conjugated polymers by incorporating 2,6-connected Azulene units into the polymeric backbone, and two conjugated copolymers P(TBAzDI-TPD) and P(TBAzDI-TFB) were designed and synthesized based on this strategy. They are the first two examples for 2,6-connected Azulene-based conjugated polymers and exhibit unipolar n-type transistor performance with an electron mobility of up to 0.42 cm2 V-1 s-1 , which is among the highest values for n-type polymeric semiconductors in bottom-gate top-contact organic field-effect transistors. Preliminary all-polymer solar cell devices with P(TBAzDI-TPD) as the electron acceptor and PTB7-Th as the electron donor display a power conversion efficiency of 1.82 %.
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application of Azulene in constructing organic optoelectronic materials new tricks for an old dog
ChemPlusChem, 2017Co-Authors: Hanshen Xin, Xike GaoAbstract:Azulene, as an isomer of naphthalene, has received increasing interest due to its unique chemical structure and unusual photophysical properties, including a large dipole moment of 1.08 D, a narrow energy gap between the HOMO and LUMO, and abnormal fluorescence (anti-Kasha's rule) from the second excited state to the ground state. In this Minireview, the general strategies and representative synthetic methods for the preparation and functionalization of Azulene and its derivatives are presented, and then the application of Azulene-based optoelectronic materials in organic field-effect transistors and solar cells is discussed. Finally, the challenges and outlook on developing Azulene-based optoelectronic materials are discussed, together with several key points on molecular design and synthesis.
