In this work, a novel version of macrocyclic arenes, namely leaning pillar[6]arenes, was discovered and it can be considered as a tilted version of a pillar[6]arene with two hydroxy/alkoxy functionalities removed. Through a facile two-step synthetic approaches, in conjunction with a diversity of post-modification possibilities, a series of leaning pillar[6]arenes, with good cavity adaptability and enhanced guest-binding capability, was synthesized, and their self-assembly in single-crystal states is presented. DFT calculations demonstrated that the lower rotational barrier of unsubstituted phenylene rings, the uneven electron density centered at the leaning phenyl rings, and the polarization effect along the edge generated by the hydrogen-bond-induced orientation of hydroxy groups greatly affected the host-guest properties, and meanwhile provided an intuitive explanation for the pillar-like and rigid structure of traditional pillar[6]arenes. Significantly, the crystal structure of cyclo-oligomeric quinone was obtained by direct oxidation of leaning pillar[6]arenes.

The introduction of B ← N coordinate bondisoelectronic to C−C single bondinto π-systems represents a promising strategy to impart exotic redox and electrochromic properties into conjugated organic molecules and macromolecules. To achieve both reductive and oxidative activities using this strategy, a cruciform ladder-type molecular constitution was designed to accommodate oxidation-active, reduction-active, and B ← N coordination units into a compact structure. Two such compounds (BN-F and BN-Ph) were synthesized via highly efficient N-directed borylation. These molecules demonstrated well-separated, two reductive and two oxidative electron-transfer processes, corresponding to five distinct yet stable oxidation states, including a rarely observed boron-containing radical cation. Spectroelectrochemical measurements revealed unique optical characteristics for each of these reduced/oxidized species, demonstrating multicolor electrochromism with excellent recyclability. Distinct color changes were observed between each redox state with clear isosbestic points on the absorption spectra. The underlying redox mechanism was elucidated by a combination of computational and experimental investigations. Single-crystal X-ray diffraction analysis on the neutral state, the oxidized radical cation, and the reduced dianion of BN-Ph revealed structural transformations into two distinct quinonoid constitutions during the oxidation and reduction processes, respectively. B ← N coordination played an important role in rendering the robust and reversible multistage redox properties, by extending the charge and spin delocalization, by modulating the π-electron density, and by a newly established hyperconjugation mechanism.

Active conformational control is realized in a conjugated system using intramolecular hydrogen bonds to achieve tailored molecular, supramolecular, and solid-state properties. The hydrogen bonding functionalities are fused to the backbone and precisely preorganized to enforce a fully coplanar conformation of the π-system, leading to short π-π stacking distances, controllable molecular self-assembly, and solid-state growth of one-dimensional nano-/microfibers. This investigation demonstrates the efficiency and significance of an intramolecular noncovalent approach in promoting conformational control and self-assembly of organic molecules.

Ladder-type conjugated molecules with a low band gap and low LUMO level were synthesized through an N-directed borylation reaction of pyrazine-derived donor-acceptor-donor precursors. The intramolecular boron-nitrogen coordination bonds played a key role in rendering the rigid and coplanar conformation of these molecules and their corresponding electronic structures. Experimental investigation and theoretical simulation revealed the dynamic nature of such coordination, which allowed for active manipulation of the optical properties of these molecules by using competing Lewis basic solvents.

Global intramolecular hydrogen bonds were installed and manipulated in a rigid artificial synthetic polymer in order to actively control its conformation for synthesis and processing. The polymer solubility was switched on and off by chemically inhibiting and regenerating these preorganized intramolecular hydrogen bonds. Such active manipulation made it possible to synthesize this highly rigid polymer with elevated molecular weights. A well-solubilized, noncoplanar polymer precursor with thermally cleavable Boc groups was synthesized (M n = 32.4 kg/mol). After processing this precursor into thin films, in situ thermal treatment regenerated the latent intramolecular hydrogen bonds and led to a rigid ladder-type conformation. Such manipulation of the intramolecular hydrogen bonds allowed for multilayer deposition of this polymer, laying the foundation for potential additive manufacturing using this strategy.