The hazards associated with the thermal decomposition of chemically incompatible sodium hydride solvent matrices are known, with reports from the 1960s detailing the inherent instability of NaH/dimethyl sulfoxide, NaH/N,N-dimethylformamide, and NaH/N,N-dimethylacetamide mixtures. However, these hazards remain underappreciated and undercommunicated, likely as a consequence of the widespread use of these NaH/solvent matrices in synthetic chemistry. We report herein detailed investigations into the thermal stability of these mixtures and studies of the formation of gaseous products from their thermal decomposition. We expect this contribution to promote awareness of these hazards within the wider scientific community, encourage scientists to identify and pursue safer alternatives, and most importantly, help to prevent incidents associated with these reactive mixtures.

An iridium pincer complex has been immobilised in the metal–organic framework NU-1000. The stable Ir-pincer modified NU-1000 is catalytically active in the hydrogenation of alkenes in condensed phase and under flow conditions.

Abstract:The C 3 -symmetric chiral propylated host-type ligands ()-tris(isonicotinoyl)-tris(propyl)-cyclotricatechylene L1 and ()-tris(4-pyridyl-4-benzoxy)-tris(propyl)-cyclotricatechylene L2

Pd3L2 metallo-cryptophane cages with cyclotriveratrylene-type L ligands can be stabilized by use of a bis-N-heterocyclic carbene as an auxiliary cis-protecting ligand, while use of more common protecting chelating ligands such as ethylenediamine saw a Pd3L2 to Pd6L8 rearrangement occur in solution. The crystalline Pd3L2 complexes act as sponges, taking up 1,2-dichorobenzene or iodine in a single-crystal-to-single-crystal fashion despite not exhibiting conventional porosity.

Artificial photosynthetic systems for solar energy conversion exploit both covalent and supramolecular chemistry to produce favorable arrangements of light-harvesting and redox-active chromophores in space. An understanding of the interplay between key processes for photosynthesis, namely light-harvesting, energy transfer, and photoinduced charge separation and the design of novel, self-assembling components capable of these processes are imperative for the realization of multifunctional integrated systems. We report our investigations on the potential of extended tetracationic cyclophane/perylene diimide systems as components for artificial photosynthetic applications. We show how the selection of appropriate heterocycles, as extending units, allows for tuning of the electron accumulation and photophysical properties of the extended tetracationic cyclophanes. Spectroscopic techniques confirm energy transfer between the extended tetracationic cyclophanes and perylene diimide is ultrafast and quantitative, while the heterocycle specifically influences the energy transfer related parameters and the acceptor excited state.

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Crystalline M(3)L(2) complexes with either single cage or triply interlocking [2]catenane chiral structures are formed the self-assembly of host-like ligands with transition metals.

A review of the emerging field of cyclotriveratrylene-derived coordination cages is presented. Ligand-functionalised cyclotriveratrylene (CTV) derivatives self-assemble with a range of metal cations to afford coordination cages, polymers and topologically non-trivial constructs, such as [2]catenanes and a self-entangled cube. Increased control over their self-assembly allows for the controlled and predictable formation of well-defined coordination cages for application in host-guest and recognition chemistry, with surfactant binding and single-crystal-to-single-crystal (SCTSC) uptake of small-molecule guests being observed.