Quadrupolar dinuclear hypervalent tin(iv) compounds with near-infrared emission consisting of Schiff bases based on π-conjugated scaffolds.

Since π-conjugated molecules are commonly used as a scaffold for constructing optoelectronic and functional materials, much effort has been devoted to exploring novel molecular scaffolds for obtaining superior properties. This study focuses on dinuclear hypervalent tin(iv) compounds prepared by the ladderization of Schiff bases using hypervalent tin units. The optical measurements found that introducing hypervalent tin atoms can reinforce the D-π-A system. We synthesized two types of dinuclear hypervalent compounds by simple condensation reactions and observed near-infrared (NIR) emission. Also, depending on the direction of the imine bonds, these molecules had different quadrupolar orientations with D-π-A-π-D and A-π-D-π-A systems followed by negative solvatochromism, which is the unique behavior of quadrupolar-derived absorption. Furthermore, the π-conjugated polymers involving dinuclear compounds showed NIR emission in the wavelength range over 800 nm owing to the distinct expansion of π-conjugation. Our findings could be useful not only for constructing electronic structures with narrow energy gaps but also for designing molecules with unique electronic states and environmental responsiveness.