Influence of Intermolecular Structural Effects on Radiative Efficiency in Xanthene-Based Carboranyl Luminophores

Abstract

Two o-carboranes with (i) 9,9-dimethyl-9H-xanthene and (ii) spiro[fluorene-9,9′-xanthene] moieties (XTC and sXTC, respectively) were prepared and characterized. Single X-ray crystallography analysis revealed the presence of intermolecular hydrogen bonds in XTC crystals. Although both compounds did not exhibit emission in tetrahydrofuran solutions at 298 K, intense bluish emission was observed in the solid states and frozen tetrahydrofuran solutions at 77 K. According to the results of theoretical calculations, this emission originated from an intramolecular charge transfer (ICT) transition with the o-carborane moiety. The absolute quantum efficiency (Φ em ) of the ICT-based emission in the film state equaled 49% for XTC and 20% for sXTC but was as high as 90% for the crystals of both compounds. The crystal structures of XTC and sXTC revealed that the o-carboranylappended phenyl plane was orthogonal (85−89°) to the carbon−carbon bonding axis in the o-carborane, indicating the existence of a strong exo-π-interaction, which was identified as the structural basis for the ICT-based transition. These results implied that the intermolecular structural effect of XTC in the randomly aggregated solid state (film) helped maintain the above orthogonality and, hence, the high efficiency from the ICT radiative mechanism. Thus, we concluded that the ICT radiative efficiency of o-carboranyl luminophores in the aggregated solid state can be controlled by specific intermolecular interactions and that the molecular geometric design inducing this feature can be important for developing highly efficient carboranyl luminophores.