6380-34-3Relevant academic research and scientific papers
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.
Dibenzoarsacrowns: an experimental and computational study on the coordination behaviors
Sumida, Akifumi,Kobayashi, Ryosuke,Yumura, Takashi,Imoto, Hiroaki,Naka, Kensuke
, p. 2013 - 2016 (2021)
Dibenzoarsacrowns have been synthesized as a novel class of heteroatom-fused crown ethers. The dibenzoarsacrowns can size-selectively capture alkali metal cations, and the arsenic atoms chemoselectively coordinated to gold(i) chloride (AuCl) due to the soft Lewis acid-base interaction. It is notable that the AuCl complex of 21-dibenzoarsacrown-7 further encapsulated Na+with the enhanced association constant from bare 21-dibenzoarsacrown-7. The positive allosteric effect was studied computationally.
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.
Dibenzoarsepins: Planarization of 8π-Electron System in the Lowest Singlet Excited State
Kawashima, Ikuo,Imoto, Hiroaki,Ishida, Masatoshi,Furuta, Hiroyuki,Yamamoto, Shunsuke,Mitsuishi, Masaya,Tanaka, Susumu,Fujii, Toshiki,Naka, Kensuke
, p. 11686 - 11690 (2019)
Dibenzo[b,f]arsepins possessing severely distorted cores compared to those of other heteropins were synthesized. These derivatives exhibited dual photoluminescence in the green-to-red region (500–700 nm) and the near-ultraviolet region (1) state. The computational approach for the assessment of the aromatic indices revealed that the dibenzoarsepins studied show aromaticity (8π system) in the S1 states in line with Baird's rule. The lone pair electrons of the arsenic atoms play a crucial role in the aromaticity in the S1 states.
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.
Phenyldiquinolinylarsine as a Nitrogen-Arsenic-Nitrogen Pincer Ligand
Kihara, Hyota,Tanaka, Susumu,Imoto, Hiroaki,Naka, Kensuke
supporting information, p. 3662 - 3665 (2020/08/26)
A nitrogen-arsenic-nitrogen (NAN) ligand, phenyldiquinolinylarsine (pdqa), was newly synthesized by utilizing diiodophenylarsine as a key precursor. The copper(I) halide (CuX, X = Cl, Br, I) and gold(I) chloride (AuCl) complexes of pdqa were synthesized and their structures were analyzed by NMR spectroscopy and X-ray crystallography. [CuX(pdqa)] formed pincer complexes, while only the arsenic atom coordinated to the AuI ion in [AuCl(pdqa)]. Moreover, it was found that steric strain for forming the pincer coordination was relieved around the arsenic atom, which had less directional coordination, when comparing the structure of a CuI complex with bidentate ligand diphenylquinolinylarsine.
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).
A practical screening strategy of arsenic ligands for a transition-metal-catalyzed reaction
Imoto, Hiroaki,Yamazawa, Chieko,Tanaka, Susumu,Kato, Takuji,Naka, Kensuke
supporting information, p. 821 - 823 (2017/06/13)
Organoarsenic ligands were synthesized via a safe and easy procedure, superior to the conventional synthetic methodologies. Diiodophenylarsine was prepared in situ, and was readily converted to diarylphenylarsines. Pd-catalyzed Mizoroki-Heck reaction was investigated using the obtained arsenic ligands. It was found that bulky and electron-donating ligands were effective for the reaction, meaning that the success in the screening of arsenic ligand structures was based on the present facile strategy.
An experimental study on arsoles: Structural variation, optical and electronic properties, and emission behavior
Ishidoshiro, Makoto,Imoto, Hiroaki,Tanaka, Susumu,Naka, Kensuke
, p. 8717 - 8723 (2016/06/09)
We experimentally demonstrated the intrinsic nature of arsoles as promising functional heteroles. A series of 2,5-diarylarsoles are easily and safely prepared through the procedure in which non-volatile arsenic intermediates are employed to overcome the synthetic barrier due to the concern of volatility of the arsenic precursors used in conventional methods. A Pd-catalyzed Suzuki-Miyaura coupling reaction can be applied to the obtained arsoles for fine molecular design, unlikely to phospholes. It was demonstrated that the optical and electronic properties, i.e. emission colors, quantum yields, and energy levels of the frontier orbitals, are similar to those of phospholes, as conventional theoretical studies have predicted. Furthermore, it was found that arsoles showed mechanochromic properties.
Facile synthesis and properties of dithieno[3,2-: B:2′,3′- d] arsoles
Kato, Takuji,Imoto, Hiroaki,Tanaka, Susumu,Ishidoshiro, Makoto,Naka, Kensuke
, p. 11338 - 11345 (2016/07/26)
Dithieno[3,2-b:2′,3′-d]arsoles have been synthesized via a safe and easy synthetic procedure, in which volatile arsenic intermediates are excluded. The obtained dithienoarsole derivatives were stable in the ambient atmosphere, unlike their phosphorus analogues, dithienophospholes. The Suzuki-Miyaura coupling reaction is applicable for structural modification and expansion of the π-conjugated system, and carried out the polymerization of the compounds. Dithienoarsoles showed an intense emission not only in solution but also in the solid state, and their molecular packing was analyzed by X-ray crystallography. The main-chain type dithienoarsole polymer formed a luminescent film. This work has demonstrated that dithienoarsole is a promising building block for luminescent materials.
