Photo-controllable heterostructured crystals of metal-organic frameworks via reversible photocycloaddition.

Metal-organic framework (MOF)-based heterostructures are attractive because they can provide versatile platforms for various applications but are limited by complex liquid epitaxial growth methods. Here, we employ photolithography to fabricate and control MOF-based heterostructured crystals via [4 + 4] photocycloaddition. A layered dysprosium-dianthracene framework, [Dy(NO3)3(depma2)1.5]·(depma2)0.5 (2) [depma2 = pre-photodimerized 9-diethylphosphonomethylanthracene (depma)] underwent a single-crystal-to-single-crystal transition at 140 °C to form [Dy(NO3)3(depma)(depma2)]·(depma2)0.5 (3). The dissociated anthracene moieties are face-to-face π-π interacted allowing a reversible photocycloaddition between 2 and 3. This structural transformation causes a luminescence switch between blue and yellow-green and thus can be used to fabricate erasable 2 + 3 heterostructured crystals for rewritable photonic barcodes. The internal strain at the heterostructure interface leads to photobending and straightening of the crystal, a photomechanical response that is fast, reversible and durable, even operating at 140 °C, making it promising for photoactuation. This work may inspire the development of intelligent MOF-based heterostructures for photonic applications.

From helices to superhelices: hierarchical assembly of homochiral van der Waals 1D coordination polymers.

Chiral transcription from the molecular level to the macroscopic level by self-organization has been a topic of considerable interest for mimicking biological systems. Homochiral coordination polymers (CPs) are intriguing systems that can be applied in the construction of artificial helical architectures, but they have scarcely been explored to date. Herein, we propose a new strategy for the generation of superhelices of 1D CPs by introducing flexible cyclohexyl groups on the side chains to simultaneously induce interchain van der Waals interactions and chain misalignment due to conformer interconversion. Superhelices of S- or R-Tb(cyampH)3·3H2O (S-1H, R-1H) [cyampH2 = S- or R-(1-cyclohexylethyl)aminomethylphosphonic acid] were obtained successfully, the formation of which was found to follow a new type of "chain-twist-growth" mechanism that had not been described previously. The design strategy used in this work may open a new and general route to the hierarchical assembly and synthesis of helical CP materials.