1,2,5-Triarylcycloalka[c]arsoles: Structural Effects of Fused-cycloalkanes on Stability and Photophysical Properties.

Herein, we have synthesized a variety of cycloalkane-fused arsoles. Cyclopentane and cyclohexane were incorporated into the cycloalkane-fused arsoles. Surprisingly, cyclohexane-fused arsole 2 a gradually decomposed via oxidative ring-opening under ambient conditions, while cyclopentane-fused 1 a was stable. In addition, the Stokes shift of 2 a (7766 cm-1 ) is larger than that of 1 a (5120 cm-1 ). The effects of the fused cycloalkane on the stability and photophysical properties were attributed to the distortion of the cycloalkane. Computational calculations demonstrated that the cyclohexane moiety in 2 a was frustrated upon being incorporated into the rigid arsole ring, while the cyclopentane moiety in 1 a was much less distorted.

4-Aryldithieno[3,2-b:2',3'-d]arsoles: effects of the As-substituent on the structure, photophysical properties, and stability.

Dithieno[3,2-b:2',3'-d]arsole (DTA) is one of the representative arsenic-containing conjugated units. In this work, the effects of the As-substituent on the structure, photophysical properties, and stability were investigated. Surprisingly, the As-substituent affected the structural relaxation and stability in the photo-excited state, while there was negligible effect in the ground state. Bulky substituents resulted in red-shifted emissions due to the relaxation of steric repulsion upon photo-excitation. In addition, the crystal structure highly affected the photo-degradation behaviors.