Crystal packing and photoelectric property of bis(2-picolyl)amine-functionalized triarylborane and its complexes

Abstract

Organic crystalline materials are attracting increasing interest due to their promising applications in the fields of nonlinear optics (NLO), organic lasers, optical waveguides, and light-emitting transistors. In this paper, a photoelectric molecule QB was constructed through combining an electron-withdrawing unit, a triarylborane, and a metal-ligand unit of bis(2-picolyl)amine. The crystallization behavior and crystalline photoelectric properties of QB and its complexes were thoroughly studied. This compound exhibited polymorphism, and a green emitting block-like crystal and blue-emission lamellar crystal were obtained, respectively. Their different photoluminescence mechanisms were clarified through X-ray crystallographic analysis and theoretical calculations. Furthermore, the single-crystal structures of the complexes of QB coordinating with KCN and Zn(ClO4)2 were also determined. Crystal QB-KCN emitted strong blue fluorescence at 445 nm, owing to the formation of rigid 2-to-2 adduct, which could effectively suppress non-radiative transitions. Crystal QB-Zn(ClO4)2 showed very weak cyan emission due to its loose molecular packing. The electrochemical results illuminated that the metal coordination can effectively affect the electron-withdrawing ability of conjugated triarylborane, and further affect the monomolecular luminescent properties due to the intramolecular charge transfer. We believe that polymorphism and metal coordination are available means to obtain excellent crystalline photoelectric materials.