Effect of Arsenic Coordination State on the Structure, Aromaticity, and Optical Properties of Dithieno[3,2‐b:2′,3′‐d]arsoles

Abstract

A silylated derivative of 4-phenyl-dithieno[3,2-b:2′,3′-d]arsole (DTAs) was synthesized, and the effect of coordinating of DTAs compounds to Pd on their structural and optical properties was investigated. Coordination of the As to Pd was found to increase the structural aromaticity of the ring system as measured by the harmonic oscillator measure of heterocyclic [a]

Dithienothiophenes at Work: Access to Mechanosensitive Fluorescent Probes, Chalcogen-Bonding Catalysis, and Beyond

“…Moving down the pnictogens, the full collection is available, from dithieno­[3,2- b :2′,3′- d ]­arsoles 59 – 61 − over dithieno­[3,2- b :2′,3′- d ]­stiboles 62 to dithieno­[3,2- b :2′,3′- d ]­bismoles 63 and 64 . None of them is highly fluorescent, and quantum yields decrease with the atomic mass of the pnictogen; however, the LUMO levels increase.…”

Heavier pnictogens – treasures for optical electronic and reactivity tuning

“…Coordination to Pd had a more subtle effect on the optical properties of the silylated arsole (21, R = TIPS) than was seen for the analogous phosphole, with λ ab shifting by only 5 nm and emission still taking place on photoexcitation of the ligand absorption band rather than from the charge-transfer band, as was seen for the phosphole. 34 Interestingly, work by Naka and coworkers found that coordination of the non-silylated dithienoarsole (R = H) to AuCl led to a significant red shift (93 nm) in the emission spectrum of 22. 35 However, this was accompanied by a substantial decrease in PLQY (<1% compared to 7% for the uncoordinated material), whereas for the analogous phosphole material the PLQY increased from 49% to 64% on coordination to AuCl.…”

Rearrangement and redistribution reaction of Ph2PCH2TMS with PhAsCl2 or AsCl3

“…[11] Our and others efforts to further explore the coordination chemistry of arsine and arsole based ligands has led to materials with interesting optical, electronic and catalytic properties. [12][13][14][15][16]…”