Peraryl Arsoles: Practical Synthesis, Electronic Structures, and Solid‐State Emission Behaviors

Abstract

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 (λ =445 nm) gave amorphous samples with a greenish-blue emission (λ =496 nm).

From a 2,1‐Benzazaarsole to Elusive 1‐Arsanaphthalenes in One Step

“…The chemistry of various synthetically accessible aromatic heterocycles containing heavier Group 15 elements, insteado ft he "classical" nitrogen-based ones, is fairly dominated by the unsaturated organophosphorus compounds. [1][2][3][4][5] Despite recent progress involvingthe heavier congener arsenic, [6][7][8][9][10][11][12] many relatively trivial arsenic heterocycless till remain elusive despitee xhibiting remarkable physical-chemical properties. [1,13] For example,a nd in contrast to arsinine reported by Ashe [14] and 9arsaanthracene independently synthesized by Jutzi [15] and Bickelhaupt, [16] structurally characterized1-arsanaphthalenes (i.e.…”

The Dawn of Functional Organoarsenic Chemistry

“…That is, the in situ generation of diiodoarsines from cyclooligoarsines has been applied to synthesize various arsole derivatives. Substitution reactions with adequate nucleophiles lead to the corresponding arsole derivatives, such as arsafluorene, triarylarsole, dithienoarsole, and pentaarylarsole . As a result, we have attained not only proof of predicted properties, but also discovery of advanced functions.…”

“…1,2,3,4,5‐Pentaarylarsoles 5 a – c are synthesized through the reaction of diiodophenylarsine ( 4 ) and zirconacyclopentadienes by transmetalation with copper(I) chloride (Scheme ), whereas lithium and dichlorophenylarsine were previously employed to synthesize 5 a , as described in Scheme . The silole analogue, hexaphenylsilole, is a well‐known aggregation‐induced emission (AIE) dye, and the pentaarylarsoles are also AIE active.…”

“…Because the resultant solution contains no byproducts or residual additives, without isolation, asubsequentsubstitutionreactionwith adequate nucleophiles can produce the corresponding arsole derivatives. [43,[47][48][49][50][51][52] Optical and electronic properties of as eries of arsoles were experimentally examined for the first time. In addition, it has been elucidated that oxidative tolerance of trivalent arsenic atoms of the arsole derivatives is superior to that of the phosphorus analogues.…”

“…The addition of I 2 to cyclooligoarsines 1 or 2 in Et 2 O can generate diiodoarsines 3 or 4 , respectively, in situ (Scheme b). Because the resultant solution contains no byproducts or residual additives, without isolation, a subsequent substitution reaction with adequate nucleophiles can produce the corresponding arsole derivatives . Optical and electronic properties of a series of arsoles were experimentally examined for the first time.…”