Low Pressure Carbonylation of Benzyl Carbonates and Carbamates for Applications in C Isotope Labeling and Catalytic CO Reduction.

Herein, we report a methodology to access isotopically labeled esters and amides from carbonates and carbamates employing an oxygen deletion strategy. This methodology utilizes a decarboxylative carbonylation approach for isotope labeling with near stoichiometric, ex situ generated C, or C carbon monoxide. This reaction is characterized by its broad scope, functional group tolerance, and high yields, which is showcased with the synthesis of structurally complex molecules.

"Dynamical Docking" of Cyclic Dinuclear Au(I) Bis-N-heterocyclic Complexes Facilitates Their Binding to G-Quadruplexes.

With the aim to improve the design of metal complexes as stabilizers of noncanonical DNA secondary structures, namely, G-quadruplexes (G4s), a series of cyclic dinuclear Au(I) N-heterocyclic carbene complexes based on xanthine and benzimidazole ligands has been synthesized and characterized by various methods, including X-ray diffraction. Fluorescence resonance energy transfer (FRET) and CD DNA melting assays unraveled the compounds' stabilization properties toward G4s of different topologies of physiological relevance. Initial structure-activity relationships have been identified and recognize the family of xanthine derivatives as those more selective toward G4s versus duplex DNA.

The structural complexity of perovskites.

A recent research direction related to ABX perovskites is the use of molecules on the A and/or X-site, a development that has proved fruitful for photovoltaics, (improper) ferroelectrics and barocalorics. Replacing atoms by molecules increases the chemical space for the synthesis of materials with new properties, conceptually translating chemical, synthetic freedom to novel opportunities in material design. Here an information theory-based rating scheme is applied to obtain structural complexities across various perovskite classes.

: complexity and configurational entropy of crystal structures via information theory.

The information content of a crystal structure as conceived by information theory has recently proved an intriguing approach to calculate the complexity of a crystal structure within a consistent concept. Given the relatively young nature of the field, theory development is still at the core of ongoing research efforts. This work provides an update to the current theory, enabling the complexity analysis of crystal structures with partial occupancies as frequently found in disordered systems.

Activation of Molecular Oxygen by a Cobalt(II) Tetra-NHC Complex*.

The first dicobalt(III) μ -peroxo N-heterocyclic carbene (NHC) complex is reported. It can be quantitatively generated from a cobalt(II) compound bearing a 16-membered macrocyclic tetra-NHC ligand via facile activation of dioxygen from air at ambient conditions. The reaction proceeds via an end-on superoxo intermediate as demonstrated by EPR studies and DFT.