Diradicals as Topological Charge Carriers in Metal-Organic Toy Model Pt(HIB).

We explore the eclipsed stacking of a metal-organic Kagome lattice containing heavy-metal nodes. Our model is Pt(HIB), a hypothetical but viable member of a well-known family of hexaaminobenzene based metal-organic frameworks (MOFs). Applying space group theory, it is shown how molecular diradicals, brought into play by a noninnocent ligand, become topologically nontrivial bands when moving in a periodic potential.

Symmetry-Shaped Singularities in High-Temperature Superconductor HS.

The superconducting critical temperature of HS ranks among the highest measured, at 203 K. This impressive value stems from a singularity in the electronic density-of-states, induced by a flat-band region that consists of saddle points. The peak sits right at the Fermi level, so that it gives rise to a giant electron-phonon coupling constant.

Conformational Gap Control in CsTaS.

Simple arguments based on orbital energies and crystal symmetry suggest the band gap of CsTaS to be suitable for solar cell photovoltaics. Here, we combine chemical theory with sophisticated calculations to describe an intricate relationship between the structure and optical properties of this material. Orbital interactions govern both the presence and nature of CsTaS's gap.

Be-Be π-Bonding and Predicted Superconductivity in MBe (M=Zr, Hf).

Beryllium, an s-block element, forms an aromatic network of delocalized Be-Be π bonds in alloys ZrBe and HfBe . This gives rise to stacked [Be ] layers with tetravalent cations in between. The [Be ] sublattice is isoelectronic and isostructural to graphite, as well as the [B] sublattice in MgB , and it bears identical manifestations of π bonding in its electronic band structure.

Metal-Organic Frameworks: Molecules or Semiconductors in Photocatalysis?

In the realm of solids, metal-organic frameworks (MOFs) offer unique possibilities for the rational engineering of tailored physical properties. These derive from the modular, molecular make-up of MOFs, which allows for the selection and modification of the organic and inorganic building units that construct them. The adaptable properties make MOFs interesting materials for photocatalysis, an area of increasing significance.

A Titanium Metal-Organic Framework with Visible-Light-Responsive Photocatalytic Activity.

The one-step synthesis and characterization of a new and robust titanium-based metal-organic framework, ACM-1, is reported. In this structure, which is based on infinite Ti-O chains and 4,4',4'',4'''-(pyrene-1,3,6,8-tetrayl) tetrabenzoic acid as a photosensitizer ligand, the combination of highly mobile photogenerated electrons and a strong hole localization at the organic linker results in large charge-separation lifetimes. The suitable energies for band gap and conduction band minimum (CBM) offer great potential for a wide range of photocatalytic reactions, from hydrogen evolution to the selective oxidation of organic substrates.

Mirrors of Bonding in Metal Halide Perovskites.

We explore the chemical bonding and band gap in the metal halide perovskites ABX (where A is a cation, B a metal dication, and X a halide) through detailed calculations and a qualitative, symmetry-based bonding analysis that moves between chemical and physical viewpoints, covering every aspect of bonding over a range of 15 eV around the band gap. We show how the gap is controlled by metal-halide orbital interactions that give rise to a characteristic mirror of bands, a bonding signpost which first shows up in turning on and off the scalar relativistic effects in computation of the band structure of CsPbBr. The mirror is made up by a Pb 6s and Br 4p combination that moves in an understandable way through the Brillouin zone, setting the valence band maximum.

Nanosheets of Nonlayered Aluminum Metal-Organic Frameworks through a Surfactant-Assisted Method.

During the last decade, the synthesis and application of metal-organic framework (MOF) nanosheets has received growing interest, showing unique performances for different technological applications. Despite the potential of this type of nanolamellar materials, the synthetic routes developed so far are restricted to MOFs possessing layered structures, limiting further development in this field. Here, a bottom-up surfactant-assisted synthetic approach is presented for the fabrication of nanosheets of various nonlayered MOFs, broadening the scope of MOF nanosheets application.

Cesium's Off-the-Map Valence Orbital.

The T -symmetric [CsO ] ion, featuring Cs in an oxidation state of 9, is computed to be a minimum. Cs uses outer core 5s and 5p orbitals to bind the oxygen atoms. The valence Cs 6s orbital lies too high to be involved in bonding, and contributes to Rydberg levels only.

Establishing hierarchy: the chain of events leading to the formation of silicalite-1 nanosheets.

In applying a multi-scale spectroscopic and computational approach, we demonstrate that the synthesis of stacked zeolite silicalite-1 nanosheets, in the presence of a long-tail diquaternary ammonium salt surfactant, proceeds through a pre-organised phase in the condensed state. small-angle X-ray scattering, coupled to paracrystalline theory, and backed by electron microscopy, shows that this phase establishes its meso-scale order within the first five hours of hydrothermal synthesis. vibrational and solid-state NMR spectroscopy reveal that this meso-shaped architecture already contains some elementary zeolitic features.

One-Step Synthesis of Hierarchical ZSM-5 Using Cetyltrimethylammonium as Mesoporogen and Structure-Directing Agent.

Hierarchical ZSM-5 zeolite is hydrothermally synthesized in a single step with cetyltrimethylammonium (CTA) hydroxide acting as mesoporogen and structure-directing agent. Essential to this synthesis is the replacement of NaOH with KOH. An in-depth solid-state NMR study reveals that, after early electrostatic interaction between condensed silica and the head group of CTA, ZSM-5 crystallizes around the structure-directing agent.

On Layered Silicates and Zeolitic Nanosheets.

Zeolite synthesis: In a Communication published in this journal in early 2015, Messinger, Na, Seo, Ryoo, and Chmelka (MNSRC) claim that the formation of zeolite MFI nanosheets proceeds through an intermediate, crystalline layered silicate phase. It is now proposed that the layered silicate phase in the MNSRC work is an artefact rather than a species possibly playing a significant role in MFI nanosheet formation.

Eight-coordinate fluoride in a silicate double-four-ring.

Fluoride, nature's smallest anion, is capable of covalently coordinating to eight silicon atoms. The setting is a simple and common motif in zeolite chemistry: the box-shaped silicate double-four-ring (D4R). Fluoride seeks its center.

A supramolecular strategy based on molecular dipole moments for high-quality covalent organic frameworks.

A supramolecular strategy based on strong molecular dipole moments is presented to gain access to covalent organic framework structures with high crystallinity and porosity. Antiparallel alignment of the molecules within the pore walls is proposed to lead to reinforced columnar stacking, thus affording a high-quality material. As a proof of principle, a novel pyrene dione building block was prepared and reacted with hexahydroxytriphenylene to form a boronic ester-linked covalent organic framework.

Six-coordinate Group 13 complexes: the role of d orbitals and electron-rich multi-center bonding.

Bonding in six-coordinate complexes based on Group 13 elements (B, Al, Ga, In, Tl) is usually considered to be identical to that in transition-metal analogues. We herein demonstrate through sophisticated electronic-structure analyses that the bonding in these Group 13 element complexes is fundamentally different and better characterized as electron-rich hypervalent bonding with essentially no role for the d orbitals. This characteristic is carried through to the molecular properties of the complex.

Correction: Enhancing optical absorption of metal-organic frameworks for improved visible light photocatalysis.

Correction for 'Enhancing optical absorption of metal-organic frameworks for improved visible light photocatalysis' by Maxim A. Nasalevich et al., Chem.

Molecular promoting of aluminum metal-organic framework topology MIL-101 by N,N-dimethylformamide.

In situ NMR and DFT modeling demonstrate that N,N-dimethylformamide (DMF) promotes the formation of metal-organic framework NH2-MIL-101(Al). In situ NMR studies show that upon dissociation of an aluminum-coordinated aqua ligand in NH2-MOF-235(Al), DMF forms a H-Cl-DMF complex during synthesis. This reaction induces a transformation from the MOF-235 topology into the MIL-101 topology.

Enhancing optical absorption of metal-organic frameworks for improved visible light photocatalysis.

NH2-MIL-125(Ti) has been post-synthetically functionalized with dye-like molecular fragments. The new material (methyl red-MIL-125(Ti)) exhibits improved light absorption over a wide range of the visible spectrum, and shows enhanced photocatalytic oxidation activity under visible light illumination. The consequences of functionalization and the bottlenecks in MOF photochemistry are studied in detail.