Leveraging metal node-linker self-assembly to access functional anisotropy of zirconium-based MOF-on-MOF epitaxial heterostructure thin films.

Chemically robust, functional porous materials are imperative for designing novel membranes for chemical separation and heterogeneous catalysts. Among the array of potential materials, zirconium (Zr)-based metal-organic frameworks (MOFs) have garnered considerable attention, and have been investigated for applications related to gas separation and storage, and catalysis. However, a significant challenge with Zr-MOFs lies in their processibility, particularly in achieving homogenous thin films and controlling functional anisotropy.

Noncovalent interaction guided selectivity of haloaromatic isomers in a flexible porous coordination polymer.

Porous, supramolecular structures exhibit preferential encapsulation of guest molecules, primarily by means of differences in the order of (noncovalent) interactions. The encapsulation preferences can be for geometry (dimension and shape) and the chemical nature of the guest. While geometry-based sorting is relatively straightforward using advanced porous materials, designing a "chemical nature" specific host is not.

Reply to the 'Comment on "The oxidation state in low-valent beryllium and magnesium compounds"' by S. Pan and G. Frenking, , 2022, , DOI: 10.1039/D2SC04231B.

A recent article by Pan and Frenking challenges our assignment of the oxidation state of low valent group 2 compounds. With this reply, we show that our assignment of Be(+2) and Mg(+2) oxidation states in Be(cAAC) and Mg(cAAC) is fully consistent with our data. Some of the arguments exposed by Pan and Frenking were based on visual inspection of our figures, rather than a thorough numerical analysis.

A bis-NHC-CAAC dimer derived dicationic diradical.

The isolation of carbon-centered diradicals is always challenging due to synthetic difficulties and their limited stability. Herein we report the synthesis of a -1,4-cyclohexylene bridged bis-NHC-CAAC dimer derived thermally stable dicationic diradical. The diradical character of this compound was confirmed by EPR spectroscopy.

Carbodicarbenes and Striking Redox Transitions of their Conjugate Acids: Influence of NHC versus CAAC as Donor Substituents.

Herein, a new type of carbodicarbene (CDC) comprising two different classes of carbenes is reported; NHC and CAAC as donor substituents and compare the molecular structure and coordination to Au(I)Cl to those of NHC-only and CAAC-only analogues. The conjugate acids of these three CDCs exhibit notable redox properties. Their reactions with [NO][SbF ] were investigated.

Aluminium alkyl complexes supported by imino-phosphanamide ligand as precursors for catalytic guanylation reactions of carbodiimides.

Herein, we report the synthesis, characterisation, and application of three aluminium alkyl complexes, [κ-{NHIP(Ph)NDipp}AlMe] (R = Dipp (2a), Mes (2b); Bu (2c), Dipp = 2,6-diisopropylphenyl, Mes = mesityl, and Bu = -butyl), supported by unsymmetrical imino-phosphanamide [NHIP(Ph)NDipp] [R = Dipp (1a), Mes (1b), Bu (1c)] ligands as molecular precursors for the catalytic synthesis of guanidines using carbodiimides and primary amines. All the imino-phosphanamide ligands 1a, 1b and 1c were prepared in good yield from the corresponding N-heterocyclic imine (NHI) with phenylchloro-2,6-diisopropylphenylphosphanamine, PhP(Cl)NHDipp. The aluminium alkyl complexes 2a, 2b and 2c were obtained in good yield upon completion of the reaction between trimethyl aluminium and the protic ligands 1a, 1b and 1c in a 1 : 1 molar ratio in toluene the elimination of methane, respectively.

Disclosing Cyclic(Alkyl)(Amino)Carbenes as One-Electron Reductants: Synthesis of Acyclic(Amino)(Aryl)Carbene-Based Kekulé Diradicaloids.

Herein, we disclose cyclic(alkyl)(amino)carbenes (CAACs) to be one-electron reductants under the formation of a transient radical cation as indicated by EPR spectroscopy. The disclosed CAAC reducing reactivity was used to synthesize acyclic(amino)(aryl)carbene-based Thiele and Chichibabin hydrocarbons, a new class of Kekulé diradicaloids. The results demonstrate CAACs to be potent organic reductants.

Acyclic diaminocarbene-based Thiele, Chichibabin, and Müller hydrocarbons.

Thiele, Chichibabin and Müller hydrocarbons are considered as classical Kekulé diradicaloids. Herein we report the synthesis and characterization of acyclic diaminocarbene (ADC)-based Thiele, Chichibabin, and Müller hydrocarbons. The calculated singlet-triplet energy gaps are Δ = -27.