Supramolecular chemistry

Stacking

Photochemistry

Molecule

Polymer

Organic chemistry

Amphiphile

Copolymer

Crystallography

Dimer

Chemistry

Anthracene

Accounts of Chemical Research

This Account provides a comprehensive summary of our 1-decade-long investigations into bent anthracene dimers as versatile building blocks for supramolecular capsules. The investigations initiated in 2008 with the design of an anthracene dimer with a meta-phenylene spacer bearing two substituents on the convex side. Using the bent polyaromatic building block, we began to develop novel supramolecular capsules from two different synthetic approaches. One is a coordination approach, which was pursued by converting the building block into a bent ligand with two pyridine units at the terminal positions. The ligands quantitatively assemble into an M2L4-type capsule through coordination bonding with metal ions. The other is a π-stacking approach, which was followed by utilizing the block as a bent amphiphilic molecule with two trimethylammonium groups at the spacer. In water, the amphiphiles spontaneously assemble into a micelle-type capsule through the hydrophobic effect and π-stacking interactions. Simple modification of the building block allowed us to prepare a wide variety of coordination capsules as well as π-stacking capsules, bearing different hydrophilic side-chains, terminal substitutions, connecting units, polyaromatic panels, or spacer units. The coordination capsule possesses a rigid cavity, with a diameter of ∼1 nm, surrounded by multiple anthracene panels. The spherical polyaromatic cavity binds various synthetic molecules (e.g., paracyclophanes, corannulene, BODIPY, and fullerene C60) in aqueous solutions. With the aid of the polyaromatic shell, photochemically and thermally reactive radical initiators and oligosulfurs are greatly stabilized in the cavity. Biomolecules such as hydrophilic sucrose and oligo(lactic acid)s as well as hydrophobic androgenic hormones are bound by the capsule with high selectivity. In addition, long amphiphilic poly(ethylene oxide)s are threaded into the closed shell of the capsule(s) to generate unusual pseudorotaxane-shaped host-guest complexes in water. In contrast, the π-stacking capsule furnishes a flexible cavity, adaptable to the size and shape of guest molecules, encircled by multiple anthracene panels. In water, the capsule binds hydrophobic fluorescent dyes (e.g., Nile red and DCM) in the cavity. Simple grinding of the bent amphiphile with highly hydrophobic nanocarbons such as fullerenes, nanographenes, and carbon nanotubes (followed by sonication) as well as metal-complexes such as Cu(II)-phthalocyanines and Mn(III)-tetraphenylporphyrins leads to the efficient formation of water-soluble host-guest complexes upon encapsulation. Red emission from otherwise water-deactivated Eu(III)-complexes is largely enhanced in water through encapsulation. Moreover, the incorporation of pH- and photoswitches into the amphiphile affords stimuli-responsive π-stacking capsules, capable of releasing bound guests by the addition of acid and light irradiation, respectively, in water. The host functions of the coordination and π-stacking capsules are complementary to each other, which enables selection of the capsule-type depending on the envisioned target. We are convinced that continued investigation of the present supramolecular capsules featuring the bent anthracene dimer and its derivatives will further increase their value as advanced molecular tools for synthetic, analytical, material, biological, and/or medical applications.

Bent Anthracene Dimers as Versatile Building Blocks for Supramolecular Capsules