Utilizing the π‑Acidity of Boron Subphthalocyanine To Achieve Novel Solid-State Arrangements

The ability to control the solid-state structure of organic electronic materials can have a large effect on the quality of the devices to which they are applied. In this paper, we describe the use of π–π interactions to direct the crystal structure/solid-state arrangement of boron subphthalocyanine (BsubPc) derivatives by taking advantage of the π-electron-deficiency (π-acidity) of the BsubPc molecular fragment. First, we outline why BsubPc is a π-acid by looking at its chemical characteristics and the structure of crystals formed with other π-acidic moieties. Then we show how the solid-state arrangement of BsubPc can be purposefully altered by adding π-basic substituents. We found that adding a naphthoxy substituent provides an interaction that is strong enough to direct BsubPc into a novel solid-state arrangement made up of ribbons (or catemers) of molecules linked through π-stacking interactions between the naphthoxy and neighboring BsubPc molecular fragments. A similar effect was also seen when the naphthoxy fragment was added to the stronger π-acid perfluoro-BsubPc (F12BsubPc).