In this study, various (hetero)arene-fused arsaborins were synthesized. All the synthesized arsaborins were stable under ambient conditions and allowed for the chemical modification of the lone pair of the arsenic atom. Experimental and computational studies revealed that these compounds possessed planar structures and weak anti-aromatic properties. Fluorescence with large Stokes shifts was observed due to drastic structural relaxation at 298 K, whereas intense phosphorescence due to the heavy-atom effect of arsenic was observed at 77 K. Furthermore, a thiophene-fused derivative demonstrated a temperature-dependent emission color change in the solid state, attributable to the gradual alteration in the ratio of monomer fluorescence, excimer fluorescence, and phosphorescence.
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