Poly[2(6)-aminoazulene]: synthesis, photophysical properties, and proton conductivity

Hou, Ian Cheng-Yi; Shetti, Vijayendra S.; Huang, Shou Ling; Liu, Kun-Lin; Chao, Chi-Yang; Lin, Song; Lin, You; Chen, Li Yin; Luh, T.‐Y.

doi:10.1039/c7qo00087a

Cited by 19 publications

(24 citation statements)

References 86 publications

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“…The observed spectral behavior resembles that of guaiazulene derivatives upon protonation . The occurrence and site of protonation were verified by 1 H NMR spectroscopy (Figure a,b) . Importantly, the characteristic proton signal of the 1‐position of o ‐ATE (indicated by the red number in Figure a), initially located in the aromatic region at 7.0 ppm (Figure a), disappears in o ‐ATE‐H + upon protonation (Figure b).…”

Section: Figurementioning

confidence: 57%

“…Instead, an allylic proton signal with doubled relative intensity appears at 3.9 ppm, suggesting exclusive protonation of the 1‐position. Such 1 H NMR spectral change typically indicates protonation of azulene derivatives to form tropylium species . It is worth noting that the proton signals of o ‐ATE completely vanish in the 1 H NMR spectrum of o ‐ATE‐H + (Figure b) while the S 0 →S 1 transition of azulene disappears in the UV/Vis absorption spectrum of o ‐ATE‐H + (Figure a, inset).…”

Section: Figurementioning

confidence: 95%

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Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene

et al. 2020

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Proton-responsive photochromic molecules are attractive for their ability to react on non-invasive rapid optical stimuli and the importance of protonation/deprotonation processes in various fields. Conventionally, their acidic/basic sites are on hetero-atoms, which are orthogonal to the photoactive p-center. Here, we incorporate azulene, an acid-sensitive pure hydrocarbon, into the skeleton of a diarylethene-type photoswitch. The latter exhibits a novel proton-gated negative photochromic ring-closure and its optical response upon protonation in both open and closed forms is much more pronounced than those of diarylethene photoswitches with hetero-atom based acidic/basic moieties. The unique behavior of the new photoswitch can be attributed to direct protonation on its p-system, supported by 1 H NMR and theoretical calculations. Our results demonstrate the great potential of integrating non-alternant hydrocarbons into photochromic systems for the development of multi-responsive molecular switches.

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Section: Figurementioning

confidence: 57%

Section: Figurementioning

confidence: 95%

Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene

et al. 2020

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“…synthesized 2,6‐linked polyaminoazulene ( P50 ) through Buchwald–Hartwig coupling of the corresponding monomeric carbamatoaminozulenes followed by hydrolysis. The chains of this polymer are connected by nitrogen atoms in the main chain ( Figure a), [ 65 ] which is similar to polyaniline in structure. Hou et al.…”

Section: Linear Polymersmentioning

confidence: 99%

Azulene‐Based Molecules, Polymers, and Frameworks for Optoelectronic and Energy Applications

Huang

Zhao

et al. 2020

Small Methods

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has a large dipole moment of 1.08 D. [2] By contrast, naphthalene, which only contains two fused six-membered rings, has a dipole moment of 0 D. Azulene, which was discovered and named by Piesse in 1863, has attracted considerable interest since its discovery in petroleum exploitation. [3] In 1937, Plattner and Pfau published their pioneering report on the synthesis of azulene. [4] However, their method was not practical due to its low azulene yield. In the 1950s, Ziegler and Hafner formulated a highly efficient and practical method for synthesizing azulene and its derivatives. [5] Because azulene is difficult to synthesize and has a low natural abundance, research on azulene-based molecules and materials is less advanced relative to research on its isomer. Direct functionalization of 1-and/ or 3-positions is a common and effective method of producing azulene derivatives. However, direct functionalization of other positions is much harder, e.g., bromination of 6-and 1,3-positions, [6] nucleophilic addition to obtain 6-subsituted azulene, [7] borylation at 2-position, [8] arylation at the 2-position, [9] and so on. The electron distribution in the front-line molecular orbitals (MOs) must usually be considered when functionalizing azulene. Because of resonance delocalization, the oddnumbered position of azulene, which is electron-rich, easily reacts with electrophilic compounds. Among the odd-numbered azulene varieties, 1-and 3-azulene have the highest activity. [10] By Azulene has a considerably larger dipole moment than its isomer naphthalene; it also has unique physicochemical properties, including different reactivities on five-and seven-membered rings, a dark color, a narrow gap between the highest occupied molecular orbital and lowest unoccupied molecular orbital, and stimulus response. Although azulene was discovered more than 100 years ago, the use of azulene-based derivatives can be traced back to five centuries ago. Due to its unusual structure, azulene-based molecules and materials are widely used in various fields. However, studies on azulene-based materials have long been hindered by difficulties in the synthesis. Considerably fewer studies have been conducted on azulene-based derivatives than on naphthalene-based derivatives. This perspective paper mainly introduces recent reports on the synthesis of azulene-based aromatic molecules, conjugated polymers, and coordination polymers, in addition to azulene-based frameworks. The structure-property relationship, optoelectronic applications, and energy-related applications of azulene-based derivatives are reviewed, including their use in near-infrared absorption, organic field-effect transistors, organic solar cells, and microsupercapacitors.

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“…Die beobachteten Änderungen des Spektrums ähneln denen von protonierten Guaiazulen‐Derivaten . Die Protonierung selbst und die Position der Protonierung wurde durch 1 H‐NMR‐Spektroskopie verifiziert (Abbildung a,b) . Das charakteristische Protonensignal der 1‐Position des o ‐ATE (rote Zahl in Abbildung a), das ursprünglich im aromatischen Bereich bei 7,0 ppm lag (Abbildung a), verschwindet während der Protonierung und Bildung von o ‐ATE‐H + (Abbildung b).…”

Section: Figureunclassified

“…Dies deutet auf eine ausschließliche Protonierung der 1‐Position hin. Solch eine spektrale Änderung des 1 H‐NMR‐Spektrums ist typischerweise auf die Protonierung von Azulen‐Derivaten und die einhergehende Bildung von Tropyliumspezies zurückzuführen . Zudem ist anzumerken, dass die Protonensignale von o ‐ATE im 1 H‐NMR‐Spektrum von o ‐ATE‐H + (Abbildung b) und der S 0 →S 1 Übergang von Azulen im UV/Vis‐Absorptionsspektrum von o ‐ATE‐H + verschwinden (Abbildung a, Ausschnitt).…”

Section: Figureunclassified

Protonenvermittelter Ringschluss eines negativ photochromen, Azulen‐basierten Diarylethens

et al. 2020

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Auf Protonen ansprechende photochrome Moleküle sind aufgrund ihrer Fähigkeit, auf nicht-invasive schnelle optische Stimuli zu reagieren, und wegen der ubiquitären Bedeutung von Protonierungs-und Deprotonierungsprozessen, sehr interessant. Üblicherweise befinden sich die sauren/basischen Stellen dieser Moleküle an Heteroatomen, die orthogonal zum photoaktiven p-Zentrum ausgerichtet sind. In dieser Arbeit wird Azulen, ein protonensensitiver reiner Kohlenwasserstoff, in das Gerüst eines Diarylethen-Photoschalters eingebaut. Dieser zeigt einen bisher ungekannten, protonenvermittelten, negativ photochromen Ringschluss. Veränderungen seiner optischen Eigenschaften durch Protonierung, sowohl in der offenen, als auch in der geschlossenen Form, sind viel ausgeprägter als die von Diarylethen-Photoschaltern mit Säure/Base-Gruppen auf Heteroatombasis. Das einzigartige Verhalten des neuen Photoschalters kann auf die direkte Protonierung seines p-Systems zurückgeführt werden, was sowohl durch 1 H-NMR als auch durch theoretische Berechnungen belegt wird. Unsere Ergebnisse zeigen das große Potenzial der Einbindung nicht-alternierender Kohlenwasserstoffe in photochrome Systeme für die Entwicklung von molekularen Schaltern, die auf unterschiedliche Stimuli reagieren.

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Poly[2(6)-aminoazulene]: synthesis, photophysical properties, and proton conductivity

Abstract: Dimeric aminoazulene and poly[2(6)-aminoazulene] are synthesized by Buchwald–Hartwig coupling of the corresponding monomeric carbamatoaminozulenes followed by hydrolysis.

Cited by 19 publications

References 86 publications

Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene

Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene

Azulene‐Based Molecules, Polymers, and Frameworks for Optoelectronic and Energy Applications

Protonenvermittelter Ringschluss eines negativ photochromen, Azulen‐basierten Diarylethens

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