Evolution rom [Zn] to a record-high [Zn] subblock and engineering a hierarchical supramolecular framework for enhanced iodine uptake.

Hierarchical supramolecular frameworks are being designed and constructed for various applications, yet the controlled assembly and process understanding incorporating giant building blocks remains a great challenge. Here, we report a strategy of "rivet" substitution and "hinge" linkage for the controlled assembly of the hierarchical supramolecular framework. The replacement of two "rivet" ethylene glycol (EG) molecules for triangular prism [Zn] (a small block in 1) with a 1,3-propanediol (PDO) provides space for a "hinge" linkage from adjacent ligands, thus providing a hierarchical (from micro- to mesopores, from the internal cavity to external surface) supramolecular framework (2) based on a coordinative subblock with the record number of zinc ions ([Zn]).

Supramolecular Interactions Induce Dynamics in Metal-Organic Layers to Selectively Separate Acetylene from Carbon Dioxide.

We report the synthesis and structural characterization of a 2D metal-organic framework with AB-packing layers, [Co(pybz)(CHCOO)]·DMF (, pybz= 4-(4-pyridyl)benzoate), containing a stable (4,4)-grid network fabricated by paddle-wheel nodes, ditopic pybz, and acetate ligands. After removal of the guest, the layer structure is retained but reorganized into an ABCD packing mode in the activated phase (). Consequently, the intralayer square windows (7.

Highly Enantioselective Catalysis by Enzyme Encapsulated in Metal Azolate Frameworks with Micelle-Controlled Pore Sizes.

Encapsulating enzymes within metal-organic frameworks has enhanced their structural stability and interface tunability for catalysis. However, the small apertures of the frameworks restrict their effectiveness to small organic molecules. Herein, we present a green strategy directed by visible linker micelles for the aqueous synthesis of MAF-6 that enables enzymes for the catalytic asymmetric synthesis of chiral molecules.

Mn(II) Promoted Divergent-Convergent Domino Reaction Giving Dinuclear Tetrasubstituted Pyrrole Complex.

Domino reaction of benzo[d]thiazole-2-methylamine (S1) has been developed in the presence of MnCl ⋅ 4HO, leading to tetrasubstituted pyrrole coordinated dinuclear Mn(II) complex 1 ([MnClP], P=2,3,4,5-tetrakis(benzo[d]thiazol-2-yl)pyrrol-1-ide). The reaction process has been studied by assigning a series of intermediates based on time-dependent mass spectrometry, control experiments, crystallography, and density functional theory (DFT) theoretical calculation. A plausible mechanism involving an unprecedented divergent-convergent domino sequence has been proposed.

Mechanistic insights into an NHOAc-promoted imine dance in Rh-catalysed multicomponent double C-H annulations through an N-retention/exchange dual channel.

Developing new and understanding multicomponent reactions (MCRs) is an appealing but challenging task. Herein, Rh(iii)-catalyzed multicomponent double C-H annulations of cyclic diimines (or diketones and acetone), alkynes, and ammonium acetate to assemble functionalized 1,1'-biisoquinolines and C-bridged 1,1'-bisisoquinolines with controllable N/N editing in one shot has been developed. Through a combination of isotopic-labeling (H, O, and N) experiments, crystallography, and time-dependent ESI-MS, the reaction process was studied in detail.

Multi-stage Transformations of a Cluster-Based Metal-Organic Framework: Perturbing Crystals to Glass-Forming Liquids that Re-Crystallize at High Temperature.

Glassy and liquid state metal-organic frameworks (MOFs) are emerging type of materials subjected to intense research for their rich physical and chemical properties. In this report, we obtained the first glassy MOF that involves metal-carboxylate cluster building units via multi-stage structural transformations. This MOF is composed of linear [Mn (COO) ] node and flexible pyridyl-ethenylbenzoic linker.

Monolithic Titanium Alkoxide Networks for Lithium-Ion Conductive All-Solid-State Electrolytes.

Reticular chemistry provides opportunities to design solid-state electrolytes (SSEs) with modular tunability. However, SSEs based on modularly designed crystalline metal-organic frameworks (MOFs) often require liquid electrolytes for interfacial contact. Monolithic glassy MOFs can have liquid processability and uniform lithium conduction, which is promising for the reticular design of SSE without liquid electrolytes.

Supramolecular Gel-to-Gel Transition Induced by Nanoscale Structural Perturbation via the Rotary Motion of Feringa's Motor.

Supramolecular rather than covalent molecular engineering on Feringa motors can provide an alternative toolkit for tuning the properties of motorized materials through appropriate supramolecular structural perturbations, which are underexplored. Herein, a multicomponent supramolecular gel system is successfully prepared by employing an ultra-low molecular weight gelator and a modulator-Feringa motor. The electron microscopic, spectroscopic, and rheological data revealed that the morphology and mechanical properties of the gel can be tuned via a crystallographic mismatch branching (CMB) mechanism simply by adding varied amounts of motor modulators.

Hydrazine-Halogen Exchange Strategy Toward N═N-Containing Compounds and Process Tracking for Mechanistic Insight.

An anhydride-promoted traceless hydrazine-I/Br exchange strategy is reported, where hydrazine hydrate and cyclic/linear iodonium, including rarely explored cyclic bromonium, are converted to benzo[]cinnolines/azobenzenes in one pot. The reaction proceeds through diacylation (first and second C─N formation), ,'-diarylation (third and fourth C─N formation), and deacylation/oxidation (2 C─N cleavages and 1 N═N formation). The reaction mechanism is investigated by isolating multiple intermediates and kinetic studies.

The sequential structural transformation of a heptanuclear zinc cluster towards hierarchical porous carbon for supercapacitor applications.

The peripheral N/O chelating of Schiff base ligands, inner bridges, counterions, and metal centers gave rise to a brucite disk cluster [ZnL(OCH)](NO) (Zn, (HL = 2-methoxy-6-((methylimino)-methyl)phenolate)) which crystallized into hexagonal prismatic plates. The combination of crystallographic studies, TG-MS, and other characterization techniques showed that with a fixed metal and ligand composition in the precursors, weak correlative interactions (, electrostatic interactions) and shape matching between the cluster core and counterions determine the cluster packing modes in the crystals and affect their phase and morphological changes during pyrolysis. The tracking of the pyrolysis process showed that the peripheral ligands, inner bridge, and counterion decompose first, followed by the ZnO core merging with cubic ZnO, which was then reduced by carbon and eventually evaporated, leaving behind a porous carbon structure.

Vibration assisted glass-formation in zeolitic imidazolate framework.

A new glass forming method is essential for broadening the scope of liquid and glassy metal-organic frameworks due to the limitations of the conventional melt-quenching method. Herein, we show that in situ mechanical vibration can facilitate the framework melting at a lower temperature and produce glassy metal-organic frameworks (MOFs) with unique properties. Using zeolitic imidazolate framework (ZIF)-62 as a concept-proofing material, in situ mechanical vibration enables low-temperature melting at 653 K, far below its melting point (713 K).

Short stature and melanocytic nevi in a girl with ARID1B-related Coffin-Siris syndrome: a case report.

Background: Coffin-Siris syndrome (CSS) is a rare autosomal dominant disorder characterized by intellectual disability, developmental delay, and characteristic facial features. Few patients with cutaneous phenotype in this rare syndrome have been reported.

Case Presentation: Herein, we describe a 12-year-old Chinese girl diagnosed with CSS, who was referred to our hospital because of intellectual disability and short stature.

Construction of Photo-Responsive Pd L -Type Nanocages based on Feringa's Second-Generation Motor and Its Guest Binding Ability for C.

We present the construction of a M L -type metal-organic nanocage featuring four endohedral Feringa's motor motifs and its adaptive encapsulation towards a C guest molecule. The structure of the cage, though complicated on the H NMR spectrum due to the adoption of mixed ligands, was unambiguously characterized with a combination of ESI-MS, 2D DOSY, C NMR and particularly the SAXS technique. The molecular motor within the cage demonstrated similar photophysical properties to the uncoordinated one, indicating the motor's function was not compromised when it was anchored in such a confined nanospace.

Synergistic Stimulation of Metal-Organic Frameworks for Stable Super-cooled Liquid and Quenched Glass.

Metal-organic framework (MOF) glasses are a fascinating new class of materials, yet their prosperity has been impeded by the scarcity of known examples and limited vitrification methods. In the work described in this report, we applied synergistic stimuli of vapor hydration and thermal dehydration to introduce structural disorders in interpenetrated -net MOF, which facilitate the formation of stable super-cooled liquid and quenched glass. The material after stimulus has a glass transition temperature () of 560 K, far below the decomposition temperature of 695 K.

Electronic structures of hydroxylated low index surfaces of rutile and anatase-type titanium dioxide.

Different surface planes of various types of titanium dioxide (TiO) crystals have diverse catalysis effects on the splitting of HO and H and the electronic structures of the formed hydroxylated TiO vary significantly. A series of sixteen types of hydroxylated TiO surfaces containing two types of hydroxyls (OH1 and OH2) on four kinds of low index surfaces [(001), (100), (101), and (110)] of two types of crystals [anatase (A) and rutile (R)] are studied using first-principles density functional theory calculations. The catalyzed splitting of HO and H on the eight low index surfaces is compared using Gibbs free energy.

Single-Atom Pt Boosting Electrochemical Nonenzymatic Glucose Sensing on Ni(OH)/N-Doped Graphene.

Conventional nanomaterials in electrochemical nonenzymatic sensing face huge challenge due to their complex size-, surface-, and composition-dependent catalytic properties and low active site density. In this work, we designed a single-atom Pt supported on Ni(OH) nanoplates/nitrogen-doped graphene (Pt/Ni(OH)/NG) as the first example for constructing a single-atom catalyst based electrochemical nonenzymatic glucose sensor. The resulting Pt/Ni(OH)/NG exhibited a low anode peak potential of 0.

Coordination-directed self-assembly of molecular motors: towards a two-wheel drive nanocar.

Designing and constructing hierarchical and stimuli-responsive motorized nanocar systems to perform useful tasks on-demand is highly imperative towards molecular nanotechnology. In this work, a most simplified two-wheel nanocar was successfully prepared through a facile strategy of coordination-directed self-assembly. The nanocar -AgL2 features a central pseudo square-planar Ag(I) which was bridged by two enantiomeric motors as the wheels that ensure the car moves in the same direction when observed externally.

Stepwise Increase of Nd -Based Phosphorescence by AIE-Active Sensitizer: Broadening the AIPE Family from Transition Metals to Discrete Near-Infrared Lanthanide Complexes*.

We designed two near-infrared (NIR) lanthanide complexes [(L) -Nd(NO ) ] (L=TPE -BPY for 1, TPE-BPY for 2) by employing aggregation-induced emission (AIE)-active tetraphenylethylene (TPE) derivatives as sensitizers, which possessed matched energy to Nd , prevented competitive deactivation under aggregation, even shifted the excitation window toward 600 nm by twisted intramolecular charge transfer. Furthermore, benefiting from the 4 f electron shielding effect and antenna effect, the enhanced excitation energies of the AIE-active sensitizers by structural rigidification transferred into the inert Nd excited state through LMCT, affording the first aggregation-induced phosphorescence enhancement (AIPE)-active discrete NIR-emitting lanthanide complexes. As 1 equipped with more AIE-active TPE than 2, L→Nd energy transfer efficiency in the former was higher than that in the latter under the same conditions.

Salicylaldehyde-Promoted Cobalt-Catalyzed C-H/N-H Annulation of Indolyl Amides with Alkynes: Direct Synthesis of a 5-HT3 Receptor Antagonist Analogue.

A cobalt-catalyzed annulation of the C(sp)-H/N-H bond of indoloamides with alkynes assisted by 8-aminoquinoline is reported for the synthesis of six-membered indololactams. The use of salicylaldehyde as the ligand is crucial for this transformation. The protocol has a broad scope for both alkynes and indoles.

Construction of Bulky Ligand Libraries by Ru-Catalyzed P-Assisted ortho-C-H Secondary Alkylation.

Modification of commercially available biaryl monophosphine ligands via ruthenium-catalyzed P-directed-catalyzed ortho C-H secondary alkylation is described. The use of highly ring-strained norbornene as a secondary alkylating reagent is the key to this transformation. A series of highly bulky ligands with a norbornyl group were obtained in excellent yields.

Discrete Heteropolynuclear Yb/Er Assemblies: Switching on Molecular Upconversion Under Mild Conditions.

The salts {[Ln Ln*(Hhmq) (OAc) (hfac) ] [Ln*(hfac) (OAc)(MeOH)] } (Hhmq=2-methanolquinolin-8-oxide, hfac=hexafluoroacetylacetonate; Ln, Ln*=Er, Gd, Yb) feature a discrete heteronuclear cation consisting of two types of lanthanide atoms. The quinolinoxy O-atom serves as a μ -bridge to two Ln atoms and as a μ -bridge to all three atoms, with metal⋅⋅⋅metal distances being around 3.7 Å.

Infrared, Electronic Absorption and Emission Spectra of Tris (4-methyl-1-(1- methyl-1H-benzo [d] imidazol-2-yl)-4H-benzo [d]imidazo[1,5-a]imidazol-3-yl) methyl: Roles of Molecular Electronic States and Axial Substitution.

In order to comparing and explaining the experimental infrared, electronic absorption and emission spectra of tris (4-methyl-1-(1-methyl-1H-benzo [d] imidazol-2-yl) -4H-benzo [d] imidazo[1,5-a]imidazol-3-yl) methyl (L6), density functional theory calculations were performed to systematically study the spectral properties of several species with different electronic states (L6 , L6 and HL6 ), as well as the axial substituted derivative with methoxy group (L6-OCH ). The main peaks in the vibrational, electronic absorption and emission spectra were assigned in detail. Roles of molecular electronic states and axial substitution on the spectral properties are revealed.