Application of Azulene in Constructing Organic Optoelectronic Materials: New Tricks for an Old Dog

Xin, Hanshen; Gao, Xike

doi:10.1002/cplu.201700039

Cited by 199 publications

(141 citation statements)

References 92 publications

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“…Controlo ft he moleculars tructures and physicalp roperties of polycyclic aromatic hydrocarbons (PAHs) is ac ornerstone of functionalized p-conjugations in synthetic chemistry. [1][2][3][4][5] Azulene, as an isomer of naphthalene, has received significant attention as ap romising component in the construction of functionalizedm aterials [6][7][8][9] owing to its unique photophysical and redox properties, which include al ong wavelength and weak absorption (S 0 !S 1 ), atypical fluorescence( anti-Kasha's rule, S 2 !S 0 ), and al arge dipole moment (1.08 D). The p-electron polarizationso fa zulene derived from an electron-deficient heptagona nd an electron-rich pentagone nables elective functionalizationo ft he azulene core.…”

mentioning

confidence: 99%

Construction of Polycyclic π‐Conjugated Systems Incorporating an Azulene Unit Following the Oxidation of 1,8‐Diphenyl‐9,10‐bis(phenylethynyl)phenanthrene

Konishi

Morinaga

Yasuda

2018

Chemistry A European J

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Polycyclic aromatic hydrocarbons (PAHs) that incorporate either heptagons or pentagons consist of non-planar molecular structures with unusual optoelectronic properties, and the design of a relatively simple and efficient method to construct these highly fused π-conjugated systems with odd-membered rings is in high demand. This work describes the use of silver(I) cations to promote the efficient synthesis of azulene-embedded PAH 2, which is a structural isomer of tribenzo[fg,ij,rst]pentaphene 3, via tandem oxidative transannulation between the phenyl and arylethynyl moieties. This method involves a carbophilic interaction of the silver(I) cation with the acetylene units, which facilitates an electron transfer in the initial step. The synthesized PAH 2 and the protonated cation 2 H⋅BF were fully characterized by X-ray crystallographic analysis, electronic absorption, electrochemical measurement, and quantum chemical calculation. The azulene-embedded PAH 2 exhibited a low-energy absorption band and amphoteric redox events, which were characterized as non-alternant characteristics originating from the azulene unit.

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confidence: 99%

Construction of Polycyclic π‐Conjugated Systems Incorporating an Azulene Unit Following the Oxidation of 1,8‐Diphenyl‐9,10‐bis(phenylethynyl)phenanthrene

Konishi

Morinaga

Yasuda

2018

Chemistry A European J

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“…In contrast to individual odd‐membered rings, azulene, which consists of a pair of five‐ and seven‐membered rings, is a non‐benzenoid, non‐alternant aromatic hydrocarbon . It should be noted that the topological transformation of naphthalene into azulene results in a large perturbation of the molecular symmetry and physicochemical properties .…”

Section: Figurementioning

confidence: 99%

Helical Nanographenes Containing an Azulene Unit: Synthesis, Crystal Structures, and Properties

Dmitrieva

et al. 2020

Angewandte Chemie

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Three unprecedented helical nanographenes (1, 2, and 3) containing an azulene unit are synthesized. The resultant helical structures are unambiguously confirmed by X‐ray crystallographic analysis. The embedded azulene unit in 2 possesses a record‐high twisting degree (16.1°) as a result of the contiguous steric repulsion at the helical inner rim. Structural analysis in combination with theoretical calculations reveals that these helical nanographenes manifest a global aromatic structure, while the inner azulene unit exhibits weak antiaromatic character. Furthermore, UV/Vis‐spectral measurements reveal that superhelicenes 2 and 3 possess narrow energy gaps (2: 1.88 eV; 3: 2.03 eV), as corroborated by cyclic voltammetry and supported by density functional theory (DFT) calculations. The stable oxidized and reduced states of 2 and 3 are characterized by in‐situ EPR/Vis–NIR spectroelectrochemistry. Our study provides a novel synthetic strategy for helical nanographenes containing azulene units as well as their associated structures and physical properties.

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“…In contrast, azulene, which is a structural isomer of naphthalene and possesses different photophysical properties from naphthalene due to its polarized structure, exhibits attractive redox properties . Furthermore, unlike naphthalene, whose HOMO and LUMO are distributed on all carbon atoms where substituents can be introduced, the HOMO of azulene is distributed across its odd‐positioned carbon atoms, while the coefficients of the LUMO and HOMO‐1 are greater in its even‐positioned carbons atoms (Figure ). The perturbed orbital of azulene therefore varies according to the substituent position .…”

Section: Introductionmentioning

confidence: 99%

Stereochemistry, Stereodynamics, and Redox and Complexation Behaviors of 2,2′‐Diaryl‐1,1′‐Biazulenes

Tsuchiya

Katsuoka

Yoza³

et al. 2019

ChemPlusChem

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2,2′‐Diaryl‐1,1′‐biazulenes were synthesized and electronic communication between the azulene subunits was suggested based on redox measurements. The linkage of azulene at the 1‐position also appeared to increase the HOMO levels. In addition, cyclic voltammetry measurements of 2‐arylazulenes showed a return peak associated with the oxidation, which was not observed for azulene. The stabilization of the single‐electron oxidant may be due to the SOMO‐HOMO energy inversion phenomenon. X‐ray crystallography of the azulene dimers revealed that this species possessed a syn‐type structure in which both aryl groups in the 2‐positions formed π‐stacks. The twisted structure was indicated to be in the (R)‐ or (S)‐configuration for all molecules in the unit cell. Spontaneous resolution was also shown. Furthermore, from the solid circular dichroism (CD) spectral measurements, the relationship between the absolute configuration of the molecules and the CD spectra was determined. A racemization rotational barrier of ca. 27 kcal mol−1 was calculated. Moreover, the pyridylazulene dimer cyclized upon reaction with PdCl2 to form a 3 : 3 complex, in which the biazulene units cyclized to give ratios between the (R)‐ and (S)‐forms of either 2 : 1 or 1 : 2.

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Application of Azulene in Constructing Organic Optoelectronic Materials: New Tricks for an Old Dog

Cited by 199 publications

References 92 publications

Construction of Polycyclic π‐Conjugated Systems Incorporating an Azulene Unit Following the Oxidation of 1,8‐Diphenyl‐9,10‐bis(phenylethynyl)phenanthrene

Construction of Polycyclic π‐Conjugated Systems Incorporating an Azulene Unit Following the Oxidation of 1,8‐Diphenyl‐9,10‐bis(phenylethynyl)phenanthrene

Helical Nanographenes Containing an Azulene Unit: Synthesis, Crystal Structures, and Properties

Stereochemistry, Stereodynamics, and Redox and Complexation Behaviors of 2,2′‐Diaryl‐1,1′‐Biazulenes

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