Structural Transformable Coulomb Lattice of n-Type Semiconductors for Guest Sorption.

In recent years, highly designable organic porous materials have attracted considerable attention in the development of new types of molecular adsorption-desorption materials. The adsorption-desorption process also changes the electronic structure via the existence of guest molecules. Therefore, it is possible to change the physical property during the guest adsorption-desorption cycle using an appropriate chemical design of the host crystal lattice. As the development of n-type organic semiconductors has been limited, we focused on designing an n-type organic semiconductor material to control the host crystal lattice, electronic dimensionality, chemical stability, and high electron mobility using an ionic naphthalenediimide () derivative. Low symmetrical dianionic bis(benzene--sulfonate)-naphthalenediimide (-) forms various types of single-crystal (M)(-)·(guest) with a combination of M = Na, K, Rb, and guest = HO, CHOH. Four crystals of (K)(-)·(HO), (K)(-)·(CHOH), α-(K)(-), and β-(K)(-) were transformable using the guest adsorption-desorption cycle. Two kinds of single-crystal (K)(-)·(CHOH) with = 0 and 2.0 showed a single-crystal to single-crystal (SCSC) transformation through CHOH desorption. On the contrary, five kinds of single crystals with = 0, 3.0, 3.3, 4.75, and 5.5 were identified in the single-crystal X-ray structural analyses of (K)(-)·(HO). Systematic change of the ionic radii in (M)(-) modified the crystal lattice flexibility for the guest adsorption-desorption cycles.