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.
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