We present the postmodification of a diamondoid 3D supramolecular organic framework (SOF) to append [Ru(BPY)₃]²⁺ groups through the formation of a hydrazone bond. The resulting SOF works as an efficient recyclable heterogeneous catalyst for visible-light-induced reduction of aromatic azides to amines.

A pore-expanded three-dimensional supramolecular organic framework SOF-bpb, with a previously unattained aperture size of 3.6 nm, has been constructed in water from the co-Assembly of cucurbit[8]uril (CB[8]) and a tetraphenylmethane-cored 1,4-bis(pyridin-4-yl)-benzene-Appended building block M1. The periodicity of SOF-bpb in water and in the solid state has been confirmed using synchrotron X-ray scattering and diffraction experiments. SOF-bpb can adsorb anionic and neutral Ru2+ complex photosensitizers and anionic Wells-Dawson-Type and Keggin-Type polyoxometalates (POMs). The adsorption leads to an important enrichment effect, which remarkably increases the catalytic efficiency of the Ru2+ complex-POM systems for visible light-induced reduction of protons to produce H2. The expanded aperture of SOF-bpb also facilitates light absorption of the adsorbed Ru2+ complex photosensitizers and electron transfer between excited complexes and the POM catalysts, leading to enhanced photocatalytic activities as compared with the prototypical SOF that has an aperture size of 2.1 nm.

Short DNA represents an important class of biomacromolecules that are widely applied in gene therapy, editing, and modulation. However, the development of simple and reliable methods for their intracellular delivery remains a challenge. Herein, we describe that seven water-soluble, homogeneous supramolecular organic frameworks (SOFs) with a well-defined pore size and high stability in water that can accomplish in situ inclusion of single-stranded (ss) and double-stranded (ds) DNA (21, 23, and 58 nt) and effective intracellular delivery (including two noncancerous and six cancerous cell lines). Fluorescence quenching experiments for single and double endlabeled ss- and ds-DNA support that the DNA sequences can be completely enveloped by the SOFs. Confocal laser scanning microscopy and flow cytometry reveal that five of the SOFs exhibit excellent delivery efficiencies that, in most of the studied cases, outperform the commercial standard Lipo2000, even at low SOF-nucleic acid ratios. In addition to high delivery efficiencies, the watersoluble, self-assembled SOF carriers have a variety of advantages, including convenient preparation, high stability, and in situ DNA inclusion, which are all critical for practical applications in nucleic acid delivery.