Localized Conversion of Metal–Organic Frameworks into Polymer Gels via Light-Induced Click Chemistry

The ability to control the structure and topology of polymer networks, both on macroscopic and molecular levels, is crucial for optimizing their performance. Here we describe a novel type of network polymer, which is synthesized via conversion of a highly ordered metal–organic framework (MOF) template into a polymer gel. The synthesis is performed using light-induced and metal-free thiol–ene click chemistry. The use of light-triggered reactions in combination with photomasks or other photopatterning techniques allows the reaction to be locally confined and thereby structuring the network polymer on a macroscopic level. The potential to vary and exactly adjust the parameters within the polymer network (including exact network topology on the nanometer scale as well as the macroscopic morphology) combined with the ability to further functionalize their surfaces or incorporate guest molecules allows their targeted design for potential applications in catalysis and optoelectronics as well as their use as a novel biomaterial

Rhodium–Organic Cuboctahedra as Porous Solids with Strong Binding Sites

The upbuilding of dirhodium tetracarboxylate paddlewheels into porous architectures is still challenging because of the inertness of equatorial carboxylates for ligand-exchange reaction. Here we demonstrate the synthesis of a new family of metal–organic cuboctahedra by connecting dirhodium units through 1,3-benzenedicarboxylate and assembling cuboctahedra as porous solids. Carbon monoxide and nitric oxide were strongly trapped in the internal cavity thanks to the strong affinity of unsaturated axial coordination sites of dirhodium centers

Rhodium–Organic Cuboctahedra as Porous Solids with Strong Binding Sites

The upbuilding of dirhodium tetracarboxylate paddlewheels into porous architectures is still challenging because of the inertness of equatorial carboxylates for ligand-exchange reaction. Here we demonstrate the synthesis of a new family of metal–organic cuboctahedra by connecting dirhodium units through 1,3-benzenedicarboxylate and assembling cuboctahedra as porous solids. Carbon monoxide and nitric oxide were strongly trapped in the internal cavity thanks to the strong affinity of unsaturated axial coordination sites of dirhodium centers

Integration of Porous Coordination Polymers and Gold Nanorods into Core–Shell Mesoscopic Composites toward Light-Induced Molecular Release

Besides conventional approaches for regulating in-coming molecules for gas storage, separation, or molecular sensing, the control of molecular release from the pores is a prerequisite for extending the range of their application, such as drug delivery. Herein, we report the fabrication of a new porous coordination polymer (PCP)-based composite consisting of a gold nanorod (GNR) used as an optical switch and PCP crystals for controlled molecular release using light irradiation as an external trigger. The delicate core–shell structures of this new platform, composed of an individual GNR core and an aluminum-based PCP shell, were achieved by the selective deposition of an aluminum precursor onto the surface of GNR followed by the replication of the precursor into aluminum-based PCPs. The mesoscopic structure was characterized by electron microscopy, energy dispersive X-ray elemental mapping, and sorption experiments. Combination at the nanoscale of the high storage capacity of PCPs with the photothermal properties of GNRs resulted in the implementation of unique motion-induced molecular release, triggered by the highly efficient conversion of optical energy into heat that occurs when the GNRs are irradiated into their plasmon band. Temporal control of the molecular release was demonstrated with anthracene as a guest molecule and fluorescent probe by means of fluorescence spectroscopy