Dynamic Vapochromic Behaviors of Organic Crystals Based on the Open–Close Motions of S‐Shaped Donor–Acceptor Folding Units

Abstract

The first vapochromic organic crystals are described with respect to their preparation, color change, adsorption/desorption properties, crystal structures, and color-change mechanism. Non-solvatochromic, 1,4,5,8-naphthalene-tetracarboxylic diimide (NDI) derivatives 1 a bearing two pyrrole imine (PI) tethers have been used as a motif for the crystal packing template. Red-purple vapochromic solid 3 was prepared by evacuation of orange crystals 2 (equivalent to 1 a2 MeOH), obtained by recrystallization of 1 a from MeOH. Solid 3 showed high-adsorption ability and unprecedented vapor-dependent color changes upon exposure to a variety of organic vapors, whereas light brown amorphous solid 1 a, did not show vapo- or solvatochromic behavior toward any organic solvent. The strong adsorption capability of 3 was confirmed by TGA experiments and adsorption/desorption isotherms. Analysis of the solid-state UV/Vis analysis revealed that the vapor-dependent color changes of 3 were owed to the specific interference of solvent vapors with its broad CT absorbance at lambda=450-650 nm. Packing structures of 1 a in orange crystals 2, red-purple solid 3, and regenerated orange solid 2 were unequivocally established by single crystal and synchrotron powder X-ray diffraction, respectively. Molecular structures and arrays of 1 a in these materials indicated that 1) unit 1 a had an S-shaped folded conformation in 2 and 3 by intramolecular donor-acceptor interactions between NDI and two PI units; 2) inclusion of the guest vapor into the S-shaped template decreased the intramolecular PI-NDI interactions, accompanied by increasing intermolecular NDI-NDI and PI-PI interactions; and 3) such flexible, open-close motions of the S-shaped template could be repeated during reversible adsorption/desorption processes without degradation of crystal packing. The adsorption properties and mechanism of molecular shape-dependent vapochromic behavior of 3 are discussed with reference to experimental results, crystallographic data, and theoretical calculations.