Tunable Photochromism of Spirooxazine in the Solid State: A New Design Strategy Based on the Hypochromic Effect

Abstract

As an important organic photofunctional material, spirooxazine (SO) usually does not exhibit photochromism in the solid state since the intermolecular π-π stacking impedes photoisomerization. Developing photochromic SO in the solid state is crucial for practical applications but is still full of challenges. Here, a series of spirooxazine derivatives (SO1-SO4) with bulky aromatic substituents at the 4- and 7-positions of the skeleton, which provide them with a large volume with which to undergo solid-state photochromism under mild conditions, is designed and synthesized. All the compounds SO1-SO4 exhibit tunable solid photochromism without ground colors, excellent fatigue resistance, and high thermal stability. Notably, it takes only 15 s for SO4 to reach the saturation of absorption intensity, thought to represent the fastest solid-state photoresponse of spirooxazines. X-ray crystal structures of the intermediate compound SO0 and the products SO1-SO2 as well as computational studies suggest that the bulky aromatic groups can lead to a hypochromic effect, allowing for the photochromism of SO in the solid state. The ideal photochromic properties of these spirooxazines open a new avenue for their applications in UV printing, quick response code, and related fields.