Synthesis of 3,3′-dihydroxy-2,2′-diindan-1,1′-dione derivatives for tautomeric organic semiconductors exhibiting intramolecular double proton transfer

Abstract

To investigate potential applications of the 3,3′-dihydroxy-2,2′-biindan-1,1′-dione (BIT) structure as an organic semiconductor with intramolecular hydrogen bonds, a new synthetic route under mild conditions is developed based on the addition reaction of 1,3-dione to ninhydrin and the subsequent hydrogenation of the hydroxyl group. This route affords several new BIT derivatives, including asymmetrically substituted structures that are difficult to access by conventional high-temperature synthesis. The BIT derivatives exhibit rapid tautomerization by intramolecular double proton transfer in solution. The tautomerizations are also observed in the solid state by variable temperature measurements of X-ray diffractometry and magic angle spinning ¹³C solid-state NMR. Possible interplay between the double proton transfer and the charge transport is suggested by quantum chemical calculations. The monoalkylated BIT derivative with a lamellar packing structure suitable for lateral charge transport in films shows a hole mobility of up to 0.012 cm² V⁻¹ s⁻¹ with a weak temperature dependence in an organic field effect transistor.