Pressure-Induced Emission Enhancement of Multi-Resonance o-Carborane Derivatives via Exciton‒Vibration Coupling Suppression.

Polycyclic multiple resonance (MR) molecules reveal narrowband emission, making them very promising emitters for high color purity display. Nevertheless, they still have challenges such as aggregation-induced emission quenching and spectral broadening. Overcoming these obstacles requires an in-depth understanding of the correlations among the alterations in their geometries, packing structures, and molecular vibrations and their corresponding changes in their photoluminescence (PL) properties.

Facile Construction of New Hybrid Conjugation via Boron Cage Extension.

Aromatic polycyclic systems have been extensively utilized as structural subunits for the preparation of various functional molecules. Currently, aromatics-based polycyclic systems are predominantly generated from the extension of two-dimensional (2D) aromatic rings. In contrast, polycyclic compounds based on the extension of three-dimensional (3D) aromatics such as boron clusters are less studied.

Site-Selective Functionalization of Carboranes at the Electron-Rich Boron Vertex: Photocatalytic B-C Coupling via a Carboranyl Cage Radical.

Functionalization of carboranes in a vertex-specific manner is a perennial challenge. Here, we report a photocatalytic B-C coupling for the selective functionalization of carboranes at the boron site which is most distal to carbon. This reaction was achieved by the photo-induced decarboxylation of carborane carboxylic acids to generate boron vertex-centered carboranyl radicals.

Palladium-Catalyzed Hydroboration of Alkynes with Carboranes: Facile Construction of a Library of Boron Cluster-Based AIE-Active Luminogens.

The classical aggregation-induced emission (AIE)-active luminogens (AIEgens) usually include two-dimensional aromatic systems such as tetraphenylethenes, which are synthesized in several steps by using toxic additives. Here, we proposed a new molecular design strategy for the realization of AIE properties by combining three-dimensional aromatic boron clusters of carboranes with vinyl group(s). To obtain a library of the boron cluster-based AIEgens, a Pd-catalyzed hydroboration of alkynes with carboranes is reported.

Metal-catalyzed B-H acylmethylation of pyridylcarboranes: access to carborane-fused indoliziniums and quinoliziniums.

Metal-catalyzed mono-acylmethylation of pyridylcarboranes has been realized using α-carbonyl sulfoxonium ylides as a coupling partner. The reaction features high efficiency, excellent site-selectivity and good functional group tolerance. In the presence of pyridyl and enolizable acylmethyl groups, a post-coordination mode has been proposed and validated by high resolution mass spectroscopy (HRMS) to rationalize the unique mono-substitution.

Cage···Cage Interaction: Boron Cluster-Based Noncovalent Bond and Its Applications in Solid-State Materials.

Carboranes are boron-carbon clusters with important applications in the fields of materials, catalysis, pharmaceuticals, etc. However, the noncovalent interactions that could determine the solid-state structures and properties of such boron clusters have rarely been investigated. Herein, inspired by the coordinate bond in metallacarborane or ferrocene, the boron cluster-based noncovalent interaction (denoted as cage···cage interaction) between two -carborane clusters was successfully realized by using a pyridinium-based molecular barrier.

Three types of charged ligand-based neutral phosphorescent iridium(III) complexes featuring -carborane: synthesis, structures, and solution processed organic light-emitting diode applications.

In view of the fact that coordination configurations and special functional groups are both important for the optical properties of phosphorescent iridium complex materials, we have prepared a novel family of three types of charged ligand (0, -1, and -2) based neutral phosphorescent iridium(III) complexes (Ir1-Ir4) featuring -carborane. Single crystal structures indicate that complexes (Ir2, Ir3 and Ir4) with -carborane as a functional group at different substitution sites all show a -C^C configuration between dianionic (-2) and monoanionic (-1) ligands, which are different from the -N^C configuration in complex Ir1 with -carborane as a coordination skeleton, which has an interesting Ir-B coordination bond. Notably, Ir2, Ir3 and Ir4 all show obvious yellow light emission, while Ir1 does not emit light either in solution or in the solid state.

From Mixed-Metal MOFs to Carbon-Coated Core-Shell Metal Alloy@Metal Oxide Solid Solutions: Transformation of Co/Ni-MOF-74 to CoNi@CoNiO@C for the Oxygen Evolution Reaction.

Calcination of the mixed-metal species Co/Ni-MOF-74 leads to the formation of carbon-coated CoNi@CoNiO with a metal core diameter of ∼3.2 nm and a metal oxide shell thickness of ∼2.4 nm embedded uniformly in the ligand-derived carbon matrix.

Mixed-Metal Strategy on Metal-Organic Frameworks (MOFs) for Functionalities Expansion: Co Substitution Induces Aerobic Oxidation of Cyclohexene over Inactive Ni-MOF-74.

Different amounts of Co-substituted Ni-MOF-74 have been prepared via a post-synthetic metal exchange. Inductively coupled plasma mass spectrometry, powder X-ray diffraction (XRD), N2 adsorption/desorption, and extended X-ray absorption fine structure (EXAFS) analyses indicated the successful metathesis between Co and Ni in Ni-MOF-74 to form the solid-solution-like mixed-metal Co/Ni-MOF-74. It was found that introduction of active Co into the Ni-MOF-74 framework enabled the inert Ni-MOF-74 to show activity for cyclohexene oxidation.

Noble metals can have different effects on photocatalysis over metal-organic frameworks (MOFs): a case study on M/NH₂-MIL-125(Ti) (M=Pt and Au).

M-doped NH2-MIL-125(Ti) (M=Pt and Au) were prepared by using the wetness impregnation method followed by a treatment with H2 flow. The resultant samples were characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS) analyses, N2-sorption BET surface area, and UV/Vis diffuse reflectance spectroscopy (DRS). The photocatalytic reaction carried out in saturated CO2 with triethanolamine (TEOA) as sacrificial agent under visible-light irradiations showed that the noble metal-doping on NH2-MIL-125(Ti) promoted the photocatalytic hydrogen evolution.