6380-34-3Relevant articles and documents
Arsole-Containing π-Conjugated Polymer by the Post-Element-Transformation Technique
Matsumura, Yoshimasa,Ishidoshiro, Makoto,Irie, Yasuyuki,Imoto, Hiroaki,Naka, Kensuke,Tanaka, Kazuyoshi,Inagi, Shinsuke,Tomita, Ikuyoshi
, p. 15040 - 15043 (2016)
A synthetic method to obtain an arsole-containing π-conjugated polymer by the post-transformation of the organotitanium polymer titanacyclopentadiene-2,5-diyl unit with an arsenic-containing building block is described. The UV/Vis absorption maximum and onset of the polymer were observed at 517 nm and 612 nm, respectively. The polymer exhibits orange photoluminescence with an emission maximum (Emax) of 600 nm and the quantum yield (Φ) of 0.05. The polymer proved to exhibit a quasi-reversible redox behavior in its cyclic voltammetric (CV) analysis. The energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were estimated to be ?5.43 and ?3.24 eV, respectively, from the onsets for oxidation and reduction signals in the CV analysis. Further chemical modification of the arsole unit in the π-conjugated polymer by complexation of gold(I) chloride occurred smoothly resulting in the bathochromic shift of the UV/Vis absorption and lowering of the LUMO energy level.
In-situ iodination of organoarsenic homocycles: Facile synthesis of 9-arsafluorene
Kato, Takuji,Tanaka, Susumu,Naka, Kensuke
, p. 1476 - 1478 (2015)
We developed an in-situ iodination of organoarsenic homocycles for facile and general As-C bond formation. Quantitative in-situ generations of arsenic diiodides from organoarsenic homocycles and iodine were confirmed by 1H NMR analysis. 9-Phenyl- and 9-methyl-9-arsafluorenes were prepared by this method and their optical properties were studied.
Dithieno[3,4-b:3',4'-d]arsole: A Novel Class of Hetero[5]radialenes
Hasegawa, Yasuchika,Imoto, Hiroaki,Kitagawa, Yuichi,Naka, Kensuke,Urushizaki, Aya,Yumura, Takashi
, (2020)
[5]Radialene is known as an unstable cyclic hydrocarbon with a cross-conjugated system. Incorporation of heteroatoms into [5]radialene skeleton is an effective strategy for stabilization. Herein we synthesized dithieno[3,4-b:3',4'-d]arsole (1) as a novel class of hetero[5]radialenes since trivalent arsenic atom is much more stable than phosphorus one, which was used for hetero[5]radialene but unstable in air. The characteristic nature of the arsa[5]radialene was experimentally and computationally studied by comparing with the isomer, dithieno[3,2-b:2',3'-d]arsole (2). Structural analysis by X-ray crystallography and computational evaluation of aromaticity revealed the radialene character of 1. Interestingly, 1 showed phosphorescence though only fluorescence was observed for 2. Time-dependent density functional theory (TD-DFT) calculations implied that intersystem crossing could readily occur upon excitation for 1. Furthermore, it was computationally elucidated that dimerization and/or oligomerization via Diels-Alder reaction, which convert [5]radialene, were circumvented to offer stability for 1.
Peraryl Arsoles: Practical Synthesis, Electronic Structures, and Solid-State Emission Behaviors
Imoto, Hiroaki,Urushizaki, Aya,Kawashima, Ikuo,Naka, Kensuke
, p. 8797 - 8803 (2018/06/26)
2,3,4,5-Tetraaryl-1-phenylarsoles were synthesized by utilizing safely generated diiodophenylarsine and zirconacyclopentadienes. The obtained peraryl arsoles showed aggregation-induced emission (AIE), where intense emission was observed in the solid states (quantum yields up to 0.61), whereas the corresponding solutions were very weakly emissive. The optical and electronic properties were examined by experimental and computational methods. It was elucidated that the aryl groups at the 2,5-positions affected the frontier orbitals and the aromaticity of the arsole core. On the other hand, those at the 1,3,5-positions were perpendicular to the luminophore and effective for a restriction of aggregation-caused quenching. Because the lone pair of the arsenic atom has a sufficient coordination ability due to the low aromaticity of the arsole moiety, a gold(I) chloride complex of 1,2,3,4,5-pentaphenylarsole was synthesized. The complex formation caused a blue shift of the emission from the bare ligand. Interestingly, the complex showed luminescent mechanochromism; grinding the crystals with a blue emission (λem=445 nm) gave amorphous samples with a greenish–blue emission (λem=496 nm).
