Unlocking Solid-State Organometallic Photochemistry with Optically Transparent, Porous Salt Thin Films.

Synthetic porous materials continue to garner attention as platforms for solid-state chemistry and as designer heterogeneous catalysts. Applications in photochemistry and photocatalysis, however, are plagued by poor light harvesting efficiency due to light scattering resulting from sample microcrystallinity and poor optical penetration that arises from inner filter effects. Here we demonstrate the layer-by-layer growth of optically transparent, photochemically active thin films of porous salts.

On the mechanism of intermolecular nitrogen-atom transfer from a lattice-isolated diruthenium nitride intermediate.

Catalyst confinement within microporous media provides the opportunity to site isolate reactive intermediates, enforce intermolecular functionalization chemistry by co-localizing reactive intermediates and substrates in molecular-scale interstices, and harness non-covalent host-guest interactions to achieve selectivities that are complementary to those accessible in solution. As part of an ongoing program to develop synthetically useful nitrogen-atom transfer (NAT) catalysts, we have demonstrated intermolecular benzylic amination of toluene at a Ru nitride intermediate confined within the interstices of a Ru-based metal-organic framework (MOF), Ru(btc)X (btc = 1,3,5-benzenetricarboxylate, , Ru-HKUST-1 for X = Cl). Nitride confinement within the extended MOF lattice enabled intermolecular C-H functionalization of benzylic C-H bonds in preference to nitride dimerization, which was encountered with soluble molecular analogues.

Atomically Precise Crystalline Materials Based on Kinetically Inert Metal Ions via Reticular Mechanopolymerization.

Atomistic control of the coordination environment of lattice ions and the distribution of metal sites within crystalline mixed-metal coordination polymers remain significant synthetic challenges. Herein is reported the mechanochemical synthesis of a reticular family of crystalline heterobimetallic metal-organic frameworks (MOFs) is now achieved by polymerization of molecular Ru [II,III] complexes, featuring unprotected carboxylic acid substituents, with Cu(OAc) . The resulting crystalline heterobimetallic MOFs are solid solutions of Ru and Cu sites housed within [M L ] phases.

Palladium-Catalyzed Selective meta-C-H Deuteration of Arenes: Reaction Design and Applications.

Deuterium-labeled compounds find wide applications in kinetic studies, and within the pharmaceutical industry. An easily removable pyrimidine-based auxiliary has been employed for the meta-C-H deuteration of arenes. The scope of this Pd-catalyzed deuteration using commercially available [D ]- and [D ]-acetic acid has been demonstrated by its application in phenylacetic acid and phenylmethanesulfonate derivatives.