Impact of Donor−Acceptor Geometry and Metal Chelation on Photophysical Properties and Applications of Triarylboranes

Abstract

Three-coordinate organoboron compounds have recently found a wide range of applications in materials chemistry as nonlinear optical materials, chemical sensors, and emitters for organic light-emitting diodes (OLEDs). These compounds are excellent electron acceptors due to the empty p(pi) orbital on the boron center. When accompanied by electron donors such as amines, these molecules possess large electronic dipoles, which promote donor-acceptor charge-transfer upon excitation with light. Because of this, donor-acceptor triarylboranes are often highly luminescent both in the solid state and in solution. In this Account, we describe our research to develop donor-acceptor triarylboranes as efficient blue emitters for OLEDs. Through the use of hole-transporting donor groups such as 1-napthylphenylamines, we have prepared multifunctional triarylboranes that can act as the emissive, electron transport, or hole transport layers in OLEDs. We have also examined donor-acceptor compounds based on 2,2'-dipyridylamine or 7-azaindolyl donors, several of which have fluorescent quantum efficiencies approaching 100%. We are also investigating the chemistry of metal-containing triarylboranes. Our studies show that the electron-deficient boryl group can greatly facilitate metal-to-ligand charge-transfer transitions and phosphorescence. In addition, electronegative linker groups such as 2,2'-bipyridine can act in synergy with metal chelation to greatly improve the electron-accepting ability and Lewis acidity of triarylboranes. Donor-acceptor triarylboranes developed in our laboratory can also serve as a series of "switch-on" sensors for fluoride ions. When the donor and acceptor are linked by rigid naphthyl or nonrigid silane linkers, donor-acceptor conjugation is disrupted and charge transfer occurs primarily through space. The binding of fluoride ions to the boron center disrupts this charge transfer, activating alternative pi --> pi* transitions in the molecule and changing the emission color of the sample. More recently, we have used these nonconjugated linkers to prepare organometallic donor-acceptor triarylboranes in which fluorescence and phosphorescence can simultaneously be observed from two different chromophores in the same molecule at ambient temperature. These dual emissive molecules remain sensitive to fluoride ions, and give synergistic singlet-triplet emission responses when titrated with F(-). Fluoride ions can also act as valuable chemical probes, providing insight into the electronic structure of this new class of optoelectronic materials. We have demonstrated that donor-acceptor triarylboranes are promising materials in anion sensing and electroluminescent device applications. Nonetheless, despite our work and that of other research groups, there is still much to be learned about organometallic and multiply emissive triarylboron systems.