Complementary C3-Symmetric Donor−Acceptor Components: Cocrystal Structure and Control of Mesophase Stability

Abstract

The overlap of pi-complementary planar organic frameworks is used to direct the assembly of extended columns of alternating donor and acceptor units. The electron-rich partner, hexaalkoxytriphenylene, is a familiar mesogen, while the electron-accepting complement is mellitic triimide, a new C(3)-symmetric building block that may be readily alkylated at its periphery without compromising its electron-accepting ability. A cocrystal of examples of the two components demonstrates pi-facial overlap of the complementary aromatic surfaces. Preparation of a series of alkylated derivatives of each component allowed the study of an array of 1:1 stoichiometry mixtures. For the optimum donor-acceptor organized mesophases within this grid, temperature stability ranges of well over 100 degrees C are observed, some of which extend below room temperature. X-ray analysis confirms the formation of hexagonally packed, alternating, donor-acceptor columns within each of the observed mesophases. The dramatic effect on mesophase formation and stability engendered via donor-acceptor organization within discrete columns is discussed in terms of the interplay of forces leading to mesophase formation, and the potential to tune mesophase characteristics via manipulation of these factors.