Metal-Organic Frameworks-Based Frustrated Lewis Pairs for Selective Reduction of Nitroolefins to Nitroalkanes.

Nitroalkanes serve as essential intermediates in the synthesis of pharmaceuticals, agrochemicals, and functional materials. To date, nitroalkanes are mainly prepared from homogeneous catalysts such as noble transition metal catalysts with poor recyclability. Herein, we propose a metal-organic framework-frustrated Lewis pair (MOF-FLP) heterogeneous catalyst for selectively reducing nitroolefins to nitroalkanes under moderate reaction conditions.

Self-Assembly of Cluster-Mediated 3D Catenanes with Size-Specific Recognition Behavior.

Although interlocked three-dimensional molecules display unique properties associated with their spatial structures, their synthesis and study of their host-guest properties remain challenging. We report the formation of a novel [2]catenane, [EtN]@[(Tp*WSCuCl)(-bpype)](OTf) ([EtN][](OTf)), by self-assembly of the cluster node [Tp*WSCuCl] and the organic linker ()-1,2-diphenyl-1,2-bis(4-(pyridin-4-yl)phenyl)ethene (-bpype). Single-crystal X-ray and NMR analyses established that [] is formed by the interpenetration of two cluster-organic cages.

Introducing Frustrated Lewis Pairs to Metal-Organic Framework for Selective Hydrogenation of -Heterocycles.

Hydrogenated nitrogen heterocyclic compounds play a critical role in the pharmaceutical, polymer, and agrochemical industries. Recent studies on partial hydrogenation of nitrogen heterocyclic compounds have focused on costly and toxic precious metal catalysts. As an important class of main-group catalysts, frustrated Lewis pairs (FLPs) have been widely applied in catalytic hydrogenation reactions.

A 3D/3D hetero-interpenetrated MOF with a novel (3,9)-c net and 6-c lcy net for the fluorescence detection of carbaryl.

An exceptional Zn-based MOF material with two-fold hetero-interpenetrated nets consisting of a 3D lcy network and a novel 3D (3,9)-coordinated framework has been constructed. The Zn-based MOF exhibits a rare yellow-green fluorescence and can be used as a fluorescence sensor to detect carbaryl with a detection limit of 4.5 μM.

Flexible Vertex Engineers the Controlled Assembly of Distorted Supramolecular Tetrahedral and Octahedral Cages.

Designing and building unique cage assemblies attract increasing interest from supramolecular chemists but remain synthetically challenging. Herein, we propose the use of a flexible vertex with adjustable angles to selectively form highly distorted tetrahedral and octahedral cages, for the first time, in which the flexible vertex forms from the synergistic effect of coordination and covalent interactions. The inherent interligand angle of the vertex can be modulated by guest anions present, which allows for the fine-tuning of different cage geometries.

Heterobimetallic Cluster-Based Coordination Polymers: Assembly, Structures and Third-Order Nonlinear Optical Properties.

Reactions of (NH ) WS with CuCN, CuCN/1,2-bis(4-pyridyl)propane (bppa) or [Cu(MeCN) ]PF /bppa under different reaction conditions afforded a set of two- or three-dimensional W/Cu/S cluster-based coordination polymers including {[Et N] [WS Cu (μ-CN) (μ-I) ]} (1), [WS Cu (μ-CN) (bppa) ] (2) and {[WS Cu (bppa) ](PF ) } (3), respectively. Compound 2 can be readily formed from reaction of 1 with bppa under solvothermal conditions. Compounds 1 and 2 feature two-dimensional networks with a "sql" topology, while 3 possesses a two-fold interpenetrated three-dimensional net with a rare "reo" topology.

The Covalent and Coordination Co-Driven Assembly of Supramolecular Octahedral Cages with Controllable Degree of Distortion.

Discovering and constructing novel and fancy structures is the goal of many supramolecular chemists. In this work, we propose an assembly strategy based on the synergistic effect of coordination and covalent interactions to construct a set of octahedral supramolecular cages and adjust their degree of distortion. Our strategy innovatively utilizes the addition of sulfur atoms of a metal sulfide synthon, [EtN][Tp*WS] (), to an alkynyl group of a pyridine-containing linker, resulting in a novel vertex with low symmetry, and of Cu(I) ions.

Exogenous Photosensitizer-, Metal-, and Base-Free Visible-Light-Promoted C-H Thiolation via Reverse Hydrogen Atom Transfer.

Visible-light-driven, intramolecular C(sp)-H thiolation has been achieved without addition of a photosensitizer, metal catalyst, or base. This reaction induces the cyclization of thiobenzanilides to benzothiazoles. The substrate absorbs visible light, and its excited state undergoes a reverse hydrogen-atom transfer (RHAT) with 2,2,6,6-tetramethylpiperidine N-oxyl to form a sulfur radical.

Metabolic Investigation in Gluconacetobacter xylinus and Its Bacterial Cellulose Production under a Direct Current Electric Field.

The effects of a direct current (DC) electric field on the growth and metabolism of Gluconacetobacter xylinus were investigated in static culture. When a DC electric field at 10 mA was applied using platinum electrodes to the culture broth, bacterial cellulose (BC) production was promoted in 12 h but was inhibited in the last 12 h as compared to the control (without DC electric field). At the cathode, the presence of the hydrogen generated a strong reductive environment that is beneficial to cell growth.