Water sorption performance of the zeolitic metal azolate framework MAF-7.

Water sorption isotherms of [Zn(mtz)] (MAF-7) were collected over a wide temperature range (15-45 °C) and its water sorption performance was assessed in terms of water uptake, sorption kinetics, recyclability, and regeneration temperature. Additionally, molecular simulations were conducted to elucidate the locations of water molecules within the pore cavity of MAF-7.

Assembling molecular semiconductor composites for enhanced photocatalytic cyclohexene oxidation.

Here, a molecular semiconductor composite was assembled by integrating atomically precise Ti-oxo clusters and phosphotungstic acid (PTA) into a cocrystal system. A molecular heterojunction was demonstrated to form between the two units, which allows the charge separation efficiency to be enhanced, resulting in a two-fold increase in photocatalytic activity for cyclohexene oxidation compared to the physically mixed composite.

Inverted All-Inorganic Nanorod-Based Light-Emitting Diodes via Electrophoretic Deposition.

High performance and high stability in all-inorganic solution processed nanocrystal-based light-emitting diodes (LEDs) are highly attractive for large area devices compared to organic material-based LEDs. In this work, an inverted all-inorganic LED structure is designed to have an easy integration with thin-film transistors. Adopting robust inorganic materials such as Ni O nanoparticle films as a hole transport layer (HTL) is beneficial for the performance of LED.

A cluster-nanozyme-coenzyme system mimicking natural photosynthesis for CO reduction under intermittent light irradiation.

Natural photosynthesis utilizes solar energy to convert water and atmospheric CO into carbohydrates through all-weather light/dark reactions based on molecule-based enzymes and coenzymes, inspiring extensive development of artificial photosynthesis. However, development of efficient artificial photosynthetic systems free of noble metals, as well as rational integration of functional units into a single system at the molecular level, remain challenging. Here we report an artificial system, the assembly system of Cu cluster and cobalt terpyridine complex, that mimics natural photosynthesis through precise integration of nanozyme complexes and ubiquinone (coenzyme Q) on Cu clusters.

Light and Guest Responsive Behavior in a Porous Coordination Network Enabled by Reversible [2+2] Photocycloaddition.

Stimuli-responsive physisorbents that undergo reversible structural transformations induced by external stimuli (e.g. light, guests, or heat) offer the promise of utility in gas storage and separation.

Cross-Linking CdSO-Type Nets with Hexafluorosilicate Anions to Form an Ultramicroporous Material for Efficient CH/CO and CH/CH Separation.

A 4.6.8 topology hybrid ultramicroporous material (HUM), {[CuF(SiF)(L)]·G}, (L = 4,4'-bisimidazolylbiphenyl, G = guest molecules), 1, formed by cross-linking interpenetrated 3D four-connected CdSO-type nets with hexafluorosilicate anions is synthesized and evaluated in the context of gas sorption and separation herein.

Ultramicroporous Lonsdaleite Topology MOF with High Propane Uptake and Propane/Methane Selectivity for Propane Capture from Simulated Natural Gas.

Propane (CH) is a widely used fuel gas. Metal-organic framework (MOF) physisorbents that are CH selective offer the potential to significantly reduce the energy footprint for capturing CH from natural gas, where CH is typically present as a minor component. Here we report the CH recovery performance of a previously unreported lonsdaleite, , topology MOF, a chiral metal-organic material, [Ni(-IEDC)(bipy)(SCN)], .

Switching Adsorbent Layered Material that Enables Stepwise Capture of C Aromatics via Single-Crystal-to-Single-Crystal Transformations.

Separation of the C aromatic isomers, xylenes (PX, MX, and OX) and ethylbenzene (EB), is important to the petrochemical industry. Whereas physisorptive separation is an energy-efficient alternative to current processes, such as distillation, physisorbents do not generally exhibit strong C selectivity. Herein, we report the mixed-linker square lattice () coordination network [Zn(sba)(bis)]·DMF (, Hsba or = 4,4'-sulfonyldibenzoic acid, bis or = trans-4,4'-bis(1-imidazolyl)stilbene) and its C sorption properties.

Effect of Extra-Framework Anion Substitution on the Properties of a Chiral Crystalline Sponge.

Chiral metal-organic materials, CMOMs, are of interest as they can offer selective binding sites for chiral guests. Such binding sites can enable CMOMs to serve as chiral crystalline sponges (CCSs) to determine molecular structure and/or purify enantiomers. We recently reported on the chiral recognition properties of a homochiral cationic diamondoid, dia, network {[Ni(-IDEC)(bipy)(HO)][NO]} (-IDEC = -indoline-2-carboxylicate, bipy = 4,4'-bipyridine), .

Directing Molecular Weaving of Covalent Organic Frameworks and Their Dimensionality by Angular Control.

Although reticular chemistry has commonly utilized mutually embracing tetrahedral metal complexes as crossing points to generate three-dimensional molecularly woven structures, weaving in two dimensions remains largely unexplored. We report a new strategy to access 2D woven COFs by controlling the angle of the usually linear linker, resulting in the successful synthesis of a 2D woven pattern based on chain-link fence. The synthesis was accomplished by linking aldehyde-functionalized copper(I) bisphenanthroline complexes with bent 4,4'-oxydianiline building units.

Shape-Memory Effect Enabled by Ligand Substitution and CO Affinity in a Flexible SIFSIX Coordination Network.

We report that linker ligand substitution involving just one atom induces a shape-memory effect in a flexible coordination network. Specifically, whereas SIFSIX-23-Cu, [Cu(SiF )(L) ] , (L=1,4-bis(1-imidazolyl)benzene, SiF =SIFSIX) has been previously reported to exhibit reversible switching between closed and open phases, the activated phase of SIFSIX-23-Cu , [Cu(SiF )(L ) ] (L =2,5-bis(1-imidazolyl)pyridine), transformed to a kinetically stable porous phase with strong affinity for CO . As-synthesized SIFSIX-23-Cu , α, transformed to less open, γ, and closed, β, phases during activation.

Crystal Engineering of a Chiral Crystalline Sponge That Enables Absolute Structure Determination and Enantiomeric Separation.

Chiral metal-organic materials (CMOMs), can offer molecular binding sites that mimic the enantioselectivity exhibited by biomolecules and are amenable to systematic fine-tuning of structure and properties. Herein, we report that the reaction of Ni(NO), -indoline-2-carboxylic acid (-IDECH), and 4,4'-bipyridine (bipy) afforded a homochiral cationic diamondoid, , network, [Ni(-IDEC)(bipy)(HO)][NO], . Composed of rod building blocks (RBBs) cross-linked by bipy linkers, the activated form of adapted its pore structure to bind four guest molecules, 1-phenyl-1-butanol (1P1B), 4-phenyl-2-butanol (4P2B), 1-(4-methoxyphenyl)ethanol (MPE), and methyl mandelate (MM), making it an example of a chiral crystalline sponge (CCS).

A Robust Molecular Porous Material for C H /CO Separation.

A molecular porous material, MPM-2, comprised of cationic [Ni (AlF )(pzH) (H O) ] and anionic [Ni Al F (pzH) (H O) ] complexes that generate a charge-assisted hydrogen-bonded network with pcu topology is reported. The packing in MPM-2 is sustained by multiple interionic hydrogen bonding interactions that afford ultramicroporous channels between dense layers of anionic units. MPM-2 is found to exhibit excellent stability in water (>1 year).

Precisely Tailoring Heterometallic Polyoxotitanium Clusters for the Efficient and Selective Photocatalytic Oxidation of Hydrocarbons.

Photocatalysis is a promising yet challenging approach for the selective oxidation of hydrocarbons to valuable oxygenated chemicals with O under mild conditions. In this work, we report an atomically precise material model to address this challenge. The key to our solution is the rational incorporation of Fe species into polyoxotitanium cluster to form a heterometallic Ti Fe cocrystal.

Black Titanium-Oxo Clusters with Ultralow Band Gaps and Enhanced Nonlinear Optical Performance.

A series of catecholate-functionalized titanium-oxo clusters (TOCs), to , with atomically precise structures were synthesized and characterized, including distinctive "boat" and "chair" conformations in and , respectively. These cluster compounds are prominent for their ultralow optical band gaps, as is visually evident from the rather unusual black TOCs (B-TOCs), to . The cluster structures were found to be ultrastable with respect to air, water, organic solvents, and even acidic or basic aqueous solutions in a wide pH range (pH 0-13), owing to the stabilizing effects of catecholate and its derivatives, as well as the carboxylate ligands.

Linear Conjugated Polymers for Solar-Driven Hydrogen Peroxide Production: The Importance of Catalyst Stability.

Hydrogen peroxide (HO) is one of the most important industrial oxidants. In principle, photocatalytic HO synthesis from oxygen and HO using sunlight could provide a cleaner alternative route to the current anthraquinone process. Recently, conjugated organic materials have been studied as photocatalysts for solar fuels synthesis because they offer synthetic tunability over a large chemical space.

Two Isostructural Titanium Metal-Organic Frameworks for Light Hydrocarbon Separation.

Presented here is the light hydrocarbon separation of titanium metal-organic frameworks (Ti-MOFs). Compared with the cyclic Ti-oxo cluster (TiO(CO), ), porous structures of and (FIR = Fujian Institute Research) can effectively improve the adsorption amounts of light hydrocarbons. The introduction of different functional groups and Ti-oxo clusters with small window sizes enables them to exhibit the highly selective separation of C and C hydrocarbons versus methane in an ambient atmosphere.

Synthesis of Ag-Doped Polyoxotitanium Nanoclusters for Efficient Electrocatalytic CO Reduction.

Ag-Ti nanocomposite materials have drawn increasing research attention because of their superior catalytic properties. However, the preparation of a crystalline Ag-Ti material is an important challenge in synthetic chemistry. Herein, we report a family of atomically precise Ag-doped polyoxotitanium nanoclusters (PTCs) (-) with a size of 19.

Tetrahedral Geometry Induction of Stable Ag-Ti Nanoclusters by Flexible Trifurcate TiL Metalloligand.

A series of increasingly large silver nanoclusters with a varied combination of Archimedean and/or Platonic solid arrangements was constructed using a flexible trifurcate TiL (L = Salicylic acid or 5-fluorosalicylic acid) metalloligand: Ag@Ag@Ti (), Ag@Ti (), Ag@Ag@Ag@Ti (), Ag@Ag@Ag@Ti (), and Ag@Ag@Ti (). The silver nanoclusters are each capped by four TiL moieties, thereby forming {Ti} supertetrahedra with average edge lengths ranging from ∼8.12 Å to ∼17.

One-Pot and Postsynthetic Phenol-Thermal Synthesis toward Highly Stable Titanium-Oxo Clusters.

The synthetic approach plays a crucial role for the exploration and optimization of functional materials. As the molecular models of titanium dioxide, polyoxo-titanium clusters have undergone rapid development over past decade. Unfortunately, many of them are unstable, especially in aqueous environments, greatly limiting their applications in catalysis and environmental fields.

Acid-Controlled Synthesis of Carboxylate-Stabilized Ti -Oxo Clusters: Scaling up Preparation, Exchangeable Protecting Ligands, and Photophysical Properties.

A range of polyoxotitanium clusters (PTCs) was constructed by tuning the type of acid (inorganic and organic) in alcoholic solvents, from Ti , Ti , Ti , Ti , to Ti . After removing the tBuOH solvent, giant carboxylate-stabilized Ti -oxo clusters in which propionic acid serves as both ligand and solvent were ultimately obtained. The four labile sites in the Ti cluster core can be occupied by two formate and two propionate anions (PTC-165) or a pair of glutarate (PTC-166) or 3-methylglutarate anions (PTC-167).

Synthesis and structural characterization of a dumbbell-like phenylphosphonate-stabilized Ti-oxide cluster.

In recent years, crystalline polyoxotitanium clusters (PTCs) have attracted increasing attention as a new kind of promising crystalline material. In this work, a PTC stabilized by phenylphosphonate ligands, i.e.

Dicarboxylate Ligands Oriented Assembly of {Ti(μ-O)} Units: From Dimer to Coordination Triangles and Rectangles.

A series of dicarboxylates bridged titanium-oxo clusters with {Ti(μ-O)} building units have been synthesized through facile one-step solvothermal reactions. It is interesting to find that the geometric characteristics of the obtained supramolecular structures highly depend on the configuration of the applied dicarboxylate ligands. A linear dimeric [TiO]L complex can be constructed using flexible cyclohexanedicarboxylic acid, while the introduction of rigid 2-nitro-1,4-benzenedicarboxylic acid gives rise to a triangular [TiO]L structure.