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Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials

Metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) are open, crystalline supramolecular coordination architectures with porous facets. These chemically tailorable framework materials are the subject of intense and expansive research, and are particularly relevant in the fields of sensory materials and device engineering. As the subfield of MOF-based sensing has developed, many diverse chemical functionalities have been carefully and rationally implanted into the coordination nanospace of MOF materials. MOFs with widely varied fluorometric sensing properties have been developed using the design principles of crystal engineering and structure–property correlations, resulting in a large and rapidly growing body of literature. This work has led to advancements in a number of crucial sensing domains, including biomolecules, environmental toxins, explosives, ionic species, and many others. Furthermore, new classes of MOF sensory materials utilizing advanced signal transduction by devices based on MOF photonic crystals and thin films have been developed. This comprehensive review summarizes the topical developments in the field of luminescent MOF and MOF-based photonic crystals/thin film sensory materials.

Metal-organic frameworks: functional luminescent and photonic materials for sensing applications.

4.2.8. Reductive Coupling 3109 5. Reaction of Aromatic Compounds 3110 5.1. Electrophilic Substitutions 3110 5.2. Radical Substitution 3111 5.3. Oxidative Coupling 3111 5.4. Photochemical Reactions 3111 6. Reaction of Carbonyl Compounds 3111 6.1. Nucleophilic Additions 3111 6.1.1. Allylation 3111 6.1.2. Propargylation 3120 6.1.3. Benzylation 3121 6.1.4. Arylation/Vinylation 3121 6.1.5. Alkynylation 3121 6.1.6. Alkylation 3121 6.1.7. Reformatsky-Type Reaction 3122 6.1.8. Direct Aldol Reaction 3122 6.1.9. Mukaiyama Aldol Reaction 3124 6.1.10. Hydrogen Cyanide Addition 3125 6.2. Pinacol Coupling 3126 6.3. Wittig Reactions 3126 7. Reaction of R,â-Unsaturated Carbonyl Compounds 3127

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Hydrogen fuel is considered as the cleanest renewable resource and the primary alternative to fossil fuels for future energy supply. Sustainable hydrogen generation is the major prerequisite to realize future hydrogen economy. The electrocatalytic hydrogen evolution reaction (HER), as the vital step of water electrolysis to H2 production, has been the subject of extensive study over the past decades. In this comprehensive review, we first summarize the fundamentals of HER and review the recent state-of-the-art advances in the low-cost and high-performance catalysts based on noble and non-noble metals, as well as metal-free HER electrocatalysts. We systemically discuss the insights into the relationship among the catalytic activity, morphology, structure, composition, and synthetic method. Strategies for developing an effective catalyst, including increasing the intrinsic activity of active sites and/or increasing the number of active sites, are summarized and highlighted. Finally, the challenges, perspectives, and research directions of HER electrocatalysis are featured.

Recent Advances in Electrocatalytic Hydrogen Evolution Using Nanoparticles.

Dichromate capture: A 3D cationic metal-organic framework consisting of distorted octahedral and tetrahedral cages was constructed by using Ag(I) and 4,4'-bis(1,2,4-triazole). The complex exhibits fast exchange, high trapping capacity, and good selectivity for Cr2 O7 (2-) through single-crystal to single-crystal transformation. The complex also features a bluish violet luminescence that is distinctly quenched after Cr2 O7 (2-) exchange.

A Cationic Metal–Organic Framework Consisting of Nanoscale Cages: Capture, Separation, and Luminescent Probing of Cr2O72− through a Single‐Crystal to Single‐Crystal Process

Bis[3-(5-nitroimino-1,2,4-triazolate)]-based energetic salts were synthesized in a simple, straightforward manner. They exhibit low solubility in available solvents, high hydrolytic stability, excellent thermal stability, high density, positive heat of formation, low shock sensitivity, and excellent detonation properties. The physical and energetic properties of some salts are similar and even superior to those of RDX.

Bis[3-(5-nitroimino-1,2,4-triazolate)]-based energetic salts: synthesis and promising properties of a new family of high-density insensitive materials.

Co3O4 spinel has been widely investigated as a promising catalyst for the oxidation of volatile organic compounds (VOCs). However, the roles of tetrahedrally coordinated Co2+ sites (Co2+Td) and octahedrally coordinated Co3+ sites (Co3+Oh) still remain elusive, because their oxidation states are strongly influenced by the local geometric and electronic structures of the cobalt ion. In this work, we separately studied the geometrical-site-dependent catalytic activity of Co2+ and Co3+ in VOC oxidation on the basis of a metal ion substitution strategy, by substituting Co2+ and Co3+ with inactive or low-active Zn2+(d0), Al3+(d0), and Fe3+(d5), respectively. Raman spectroscopy, X-ray absorption fine structure (XAFS), and in situ DRIFTS spectra were thoroughly applied to elucidate the active sites of a Co-based spinel catalyst. The results demonstrate that octahedrally coordinated Co2+ sites (Co2+Oh) are more easily oxidized to Co3+ species in comparison to Co2+Td, and Co3+ are responsible for the oxidative brea...

Geometrical-Site-Dependent Catalytic Activity of Ordered Mesoporous Co-Based Spinel for Benzene Oxidation: In Situ DRIFTS Study Coupled with Raman and XAFS Spectroscopy

Elastic Sandwich-Type rGO–VS2/S Composites with High Tap Density: Structural and Chemical Cooperativity Enabling Lithium–Sulfur Batteries with High Energy Density

Nanostructured carbon materials have been extensively used for encapsulating sulfur and improving cyclic stability of lithium-sulfur (Li-S) batteries, but high carbon content and low packing density greatly limit their volumetric energy density. Herein, we present MXene-based Ti3C2T x (T x stands for the surface terminations) nanodots-interspersed Ti3C2T x nanosheet (TCD-TCS) to accomplish spatial immobilization and conversion of high-loaded sulfur species. Rich surface polar sites in TCD-TCS enhance structural integrity of the resultant electrode, while the absence of the carbon-based materials and conductive additives results in high tap density of the cathode materials. The TCD-TCS/S electrode exhibits an almost theoretical discharge capacity at a medium sulfur loading of 1.8 mg cm-2. Notably, ultrahigh volumetric capacity (1957 mAh cm-3) and high areal capacity (13.7 mAh cm-2) are synchronously achieved at a high sulfur loading of 13.8 mg cm-2. The mechanism study of sulfur evolution during discharge process highlights the importance of the integration of MXene-based nanodots and nanosheets in Li-S batteries. This proposed methodology holds great promise for the development of various high-performance energy storage materials.

Ruihu Wang

Papers

A Cationic Metal–Organic Framework Consisting of Nanoscale Cages: Capture, Separation, and Luminescent Probing of Cr2O72− through a Single‐Crystal to Single‐Crystal Process

Bis[3-(5-nitroimino-1,2,4-triazolate)]-based energetic salts: synthesis and promising properties of a new family of high-density insensitive materials.

Geometrical-Site-Dependent Catalytic Activity of Ordered Mesoporous Co-Based Spinel for Benzene Oxidation: In Situ DRIFTS Study Coupled with Raman and XAFS Spectroscopy

Elastic Sandwich-Type rGO–VS2/S Composites with High Tap Density: Structural and Chemical Cooperativity Enabling Lithium–Sulfur Batteries with High Energy Density

Ultrafine Ti3C2 MXene Nanodots-Interspersed Nanosheet for High-Energy-Density Lithium-Sulfur Batteries.