Experimental proof for emission annihilation through bond elongation at the carbon–carbon bond in o-carborane with fused biphenyl-substituted compounds

Abstract

Because of their unique luminescence properties, such as aggregation-induced emission (AIE), intense solid-state luminescence and stimuli-responsive luminochromism, aryl-substituted o-carboranes have attracted attention as a platform for developing functional optoelectronic materials. However, there still remains one fundamental issue with the detailed mechanism of solution quenching in AIE behaviors. Aryl-modified o-carboranes with AIE properties exhibit intense emission not in solution but in the solid state. According to quantum calculations and many experimental results, the elongation at the carbon–carbon bond in o-carborane in the excited state, followed by nonradiative decay, has been proposed as a main path for emission annihilation in solution. However, intramolecular rotation would simultaneously occur, and there is a possibility that emission annihilation could be induced by the combination of both bond elongation and rotation. In this study, we designed two types of biphenyl-substituted o-carboranes having fused structures at the neighbor carbon and boron atoms for fixing molecular conformation. In these molecules, bond elongation is allowed, while rotation would be prohibited. From the series of optical measurements and theoretical investigations, we proved that emission annihilation can occur through bond elongation in the absence of rotation. Moreover, we show that bond elongation could be suppressed by introducing a bulky substituent at the adjacent carbon, and emission color tuning was achieved. This is the first example, to the best of our knowledge, to prove that excitation decay can proceed only through bond elongation without electronic perturbation caused by rotation.