Tetraaryldiborane(4) Can Emit Dual Fluorescence Responding to the Structural Change around the B–B Bond

Abstract

We report the successful synthesis of tetramesityldiborane(4) (Mes4B2) through the reductive coupling of a dimesitylborinium ion. Owing to the steric protection conferred by the mesityl groups, Mes4B2 shows exceptional chemical stability and remains intact in water. Single‐crystal X‐ray analysis revealed that Mes4B2 has an orthogonal geometry, where the B–B center is completely hidden by the mesityl groups. Remarkably, Mes4B2 emits dual fluorescence at 460 and 620 nm, both in solution and in the solid state. Theoretical calculations showed that Mes4B2 in the excited S1 state adopts a twisted or planar geometry, which is responsible for the shorter‐ or longer‐wavelength fluorescence, respectively. The intensity ratio of the dual fluorescence is sensitive to the viscosity of the medium, which suggests that Mes4B2 has potential as a ratiometric viscosity sensor.

A Tetraorganyl-Alumaborane with An Al–B σ-Bond and Two Adjacent Lewis-Acidic Centers

“…In contrast, we have recently reported enhancement of the Lewis acidity of the boron atoms in pinB–BMes 2 (pin = pinacolato; Mes = 2,4,6-Me 3 C 6 H 2 ) by overlapping the two vacant p orbitals of two boron atoms . This concept was expanded to an all carbon-substituted diborane(4) ( A ; Figure ), which exhibited even higher Lewis acidity than the corresponding triarylborane and pinB–BMes 2 . , Similar carbon-substituted homodinuclear species B – F with a B–B or Al–Al single bond have also been synthesized, − although their Lewis acidity has not been reported. In contrast, the hitherto reported heterodinuclear alumaboranes G – J − are electronically stabilized by either π-electron-donating group(s), the coordination of a Lewis base, or the formation of a three-center–two-electron bond.…”