Synthesis, Structure, and Properties of Monodispersed and Highly Luminescent Organoborane Oligomers.

Abstract

Organoborane oligomers with well-defined molecular structures and high luminescence are scarce, among which those with boron not used as bridging atoms are even more so. Here, a series of well-defined ethynyl-linked or butadiynyl-linked conjugated organoborane oligomers with high fluorescence quantum yield and extinction coefficient (i.e., high brightness) were prepared by coupling different building blocks featuring dithienooxadiborepine moieties. Single crystal structures of hexyl modified dithienooxadiborepine (1a-hex) and hexyl-modified butadiynyl-linked conjugated dimer (D2-hex) not only verified the identity of the molecular structures but also revealed that the introduction of the hexyl chains distorted the molecular structures due to steric hindrance. Optical measurements showed that the absorption and emission maxima of the six oligomeric molecules bathochromic shifted with increasing numbers of repeating units. Molecules without hexyl chains emit efficient fluorescence upon photoexcitation, and the fluorescence quantum efficiency of the ethynyl-linked conjugated dimer (D1) is close to unity. Theoretical calculation results using density functional theory methods are consistent with the single crystal data, allowing a better understanding of the spectral properties. Such results indicate that the method is efficient for expanding small organoborane molecules into π-conjugated oligomers, which can be used to modulate to emit different colors with high efficiency.