Tunable Supramolecular Assembly and Photoswitchable Conversion of Cyclodextrin/Diphenylalanine‐Based 1D and 2D Nanostructures

A photocontrolled, interconvertible supramolecular 2D‐nanosheet/1D‐nanotube system was constructed through the supramolecular assembly of adamantanyl‐modified diphenylalanine with azobenzene‐bridged bis(β‐cyclodextrin). The nanosheet exhibited a greater fluorescence enhancement effect than the nanotube. Significantly, these nanosheets and nanotubes could interconvert via the photocontrolled trans/cis isomerization of azobenzene linkers in bis(β‐cyclodextrin), and this photo‐switchable one‐dimensional/two‐dimensional morphological interconversion was reversible and recyclable. This enables convenient routes to highly ordered nanostructures with various morphologies and dimensions that can be controlled by external stimuli.     

A Switchable Open/closed Polyaromatic Macrocycle that Shows Reversible Binding of Long Hydrophilic Molecules

In spite of wide‐ranging previous studies on synthetic macrocycles, the installation of open–close functions into the frameworks remains a challenge. We present a new polyaromatic macrocycle capable of switching between open and closed forms in response to external stimuli, namely, base and acid. The macrocycle, which is prepared in three steps, has a well‐defined hydrophobic cavity with a length of around 1 nm, surrounded by four pH‐responsive acridinium panels. The open and closed structures were confirmed by single‐crystal X‐ray analysis. The cylindrical cavity can bind long hydrophilic molecules up to 2.7 nm in length in neutral water and then release the bound guests through a reversible open‐to‐closed structural change upon simple addition of base.     

Dimensional Matching versus Induced-Fit Distortions: Binding Affinities of Planar and Curved Polyaromatic Hydrocarbons with a Tetragold Metallorectangle

A tetragold(I) rectangle-like metallocage containing two pyrene-bis-imidazolylidene ligands and two carbazolyl-bis-alkynyl linkers is used for the encapsulation of a series of polycyclic aromatic hydrocarbons (PAHs), including corannulene. The binding affinities obtained for the encapsulation of the planar PAHs guests in CD₂Cl₂ are found to exponentially increase with the number of π-electrons of the guest (1.3 > logK >6.6). For the bowl-shaped molecule of corannulene, the association constant is much lower than the expected one according to its number of electrons. The molecular structure of the host–guest complex formed with corannulene shows that the molecule of the guest is compressed, while the host is expanded, thus showing an interesting case of artificial mutual induced-fit arrangement.     

Efficient Room‐Temperature Phosphorescence of a Solid‐State Supramolecule Enhanced by Cucurbit[6]uril

Efficient emission of purely organic room‐temperature phosphorescence (RTP) is of great significant for potential application in optoelectronics and photobiology. Herein, we report an uncommon phosphorescent effect of organic single molecule enhanced by resulting supramolecular assembly of host–guest complexation. The chromophore bromophenyl‐methyl‐pyridinium (PY) with different counterions as guests display various phosphorescence quantum yields from 0.4 % to 24.1 %. Single crystal X‐ray diffraction results indicate that the chromophore with iodide counterion (PYI) exhibits the highest efficiency maybe due to the halogen‐bond interactions. Significantly, the nanosupramolecular assembly of PY chloride complexation with the cucurbit[6]uril gives a greatly enhanced phosphorescent quantum yield up to 81.2 % in ambient. Such great enhancement is because of the strict encapsulation of cucurbit[6]uril, which prevents the nonradiative relaxation and promotes intersystem crossing (ISC). This supramolecular assembly concept with counterions effect provides a novel approach for the improvement of RTP.