Accessing Mg-Ion Storage in VPS via Combined Cationic-Anionic Redox with Selective Bond Cleavage.

Magnesium batteries attract interest as alternative energy-storage devices because of elemental abundance and potential for high energy density. Development is limited by the absence of suitable cathodes, associated with poor diffusion kinetics resulting from strong interactions between Mg and the host structure. VPS is reported as a positive electrode material for rechargeable magnesium batteries.

Superionic lithium transport via multiple coordination environments defined by two-anion packing.

Fast cation transport in solids underpins energy storage. Materials design has focused on structures that can define transport pathways with minimal cation coordination change, restricting attention to a small part of chemical space. Motivated by the greater structural diversity of binary intermetallics than that of the metallic elements, we used two anions to build a pathway for three-dimensional superionic lithium ion conductivity that exploits multiple cation coordination environments.

Cu(I)-thioether coordination complexes based on a chiral cyclic β-amino acid ligand.

Coordination complexes, particularly metalloproteins, highlight the significance of metal-sulfur bonds in biological processes. Their unique attributes inspire efforts to synthetically reproduce these intricate metal-sulfur motifs. Here, we investigate the synthesis and characterization of copper(I)-thioether coordination complexes derived from copper(I) halides and the chiral cyclic β-amino acid trans-4-aminotetrahydrothiophene-3-carboxylic acid (ATTC), which present distinctive structural properties and ligand-to-metal ratios.

One Carbon Ring Expansion of Bipyrrole to Bipyridine Enables Access to a π-Extended, Non-innocent, Corrole-like Ligand.

A π-extended, diaza-triphenylene embedded, mono-anionic corrole analogue and its Ni complex were synthesized from a diaza-triphenylene precursor, which was obtained from a double one-carbon insertion into a naphthobipyrrole diester. Following conversion to the corresponding activated diol and acid-catalyzed condensation with pyrrole, subsequent reaction with pentafluorobenzaldehyde afforded mono-anionic, π-extended bipyricorrole-like macrocycle. Attempted Ni insertion with Ni(OAc)  ⋅ 4H O resulted an ESR active, Ni bipyricorrole radical complex, which was converted to a stable cationic Ni complex upon treatment with [(Et O) (SbCl ) ].

Synthesis, photophysical properties and photo-induced cytotoxicity of novel tris(diazatriphenylene)ruthenium (II) complex.

Novel bipyridine-based heterocyclic building block, 3,10-dichloro-benzo[f][1,10]phenanthroline and its Ruthenium(II) complex have been synthesized and fully characterized. The synthesized Ru(II)-complex is highly luminescent displaying emission at 590 nm with quantum yield of ∼0.8 in methanol.

-Type Double Doping and the Diamond-like Morphology Shift of the Zintl Phase Thermoelectric Materials: The CaASbGe (A = Na, Li; 0.06(3) ≤ ≤ 0.17(5), 0.19(1) ≤ ≤ 0.55(1), 0.13(1) ≤ ≤ 0.22(1)) System.

Five ternary and quaternary Zintl phases in the solid-solution CaASbGe (A = Na, Li; 0.06(3) ≤ ≤ 0.17(5), 0.

SrNbOF·4HO and SrNbOF·2HO: A Variant of Three-Dimensional Tungsten Bronze and a Polar Molecular Oxide Fluoride.

Crystals of two strontium niobium oxyfluorides, SrNbOF·4HO and SrNbOF·2HO, have been grown in phase pure forms via hydrothermal reactions using SrCO, NbO, and an aqueous HF solution. Single-crystal X-ray diffraction suggests that SrNbOF·4HO, crystallizing in the orthorhombic centrosymmetric space group, (No. 55), reveals a new variant of the three-dimensional tungsten bronze structure with three-, four-, and five-membered rings that are composed of corner-sharing NbO(O/F)F, NbO(O/F)F, NbO(O/F), and SrOF groups.

Catalytic and Enantioselective Control of the C-N Stereogenic Axis via the Pictet-Spengler Reaction.

An unprecedented example of a chiral phosphoric acid-catalyzed atroposelective Pictet-Spengler reaction of N-arylindoles is reported. Highly enantioenriched N-aryl-tetrahydro-β-carbolines with C-N bond axial chirality are obtained via dynamic kinetic resolution. The hydrogen bond donor introduced on the bottom aromatic ring, forming a secondary interaction with the phosphoryl oxygen, is essential to achieving high enantioselectivity.

Two Steps to Improve the Thermoelectric Performance of the CaYbAlInSb System.

A series of quaternary and quinary Zintl phase thermoelectric (TE) compounds, CaYbAlInSb (3.07(1) ≤ ≤ 4.88(2); 0.

Second-Harmonic Generation and Photoluminescence Properties of Sn(II)- and Bi(III)-Based Lone Pair Cation-Pyridine Dicarboxylate Coordination Compounds.

Lone pair cation-based novel coordination compounds Sn[(pdc)(HO)] () and (Hbpy)[Bi(pdc)(Hpdc)]·5HO () (pdc = pyridine-2,6-dicarboxylate; bpy = 4,4'-bipyridine) were synthesized through mild hydrothermal reactions. While crystallizing in the polar space group, 2, exhibits a helical chain structure consisting of SnON distorted seesaws, 2,6-pdc linkers, and water molecules, crystallizing in the centrosymmetric (CS) space group, 1̅, reveals a pseudo-3D network composed of BiON polyhedra, 2,6-pdc ligands, Hbpy cations, and isolated HO molecules. The lone cations Sn and Bi in the title compounds are in a highly deformed polyhedral environment.

Noncovalent Intermolecular Interaction in Cofacially Stacked 24π Antiaromatic Hexaphyrin Dimer.

π-π Stacking is omnipresent not only in nature but in a wide variety of practical fields applied to our lives. Because of its importance in a performance of natural and artificial systems, such as light harvesting system and working layer in device, many researchers have put intensive effort into identifying its underlying nature. However, for the case of π-π stacked systems composed of antiaromatic units, the understanding of the fundamental mechanisms is still unclear.

Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High-Performance Mid-Infrared Nonlinear Optical Materials.

To design high-performance mid-infrared (mid-IR) nonlinear optical (NLO) materials, we have focused on the combination of a heavy metal lone pair cation, Pb and mixed oxyhalides. A systematic investigation in PbO-PbCl -PbBr system led us to discover the first examples of NLO lead mixed oxyhalides, namely, Pb O Cl Br , Pb O Cl Br , and Pb O Cl Br . All the reported materials have remarkably comprehensive properties including broad IR transparency (up to 14.

Histidinium-Driven Chirality Control of Self-Assembled Hybrid Molybdenum Oxyfluorides.

Exploring macroscopic chiral materials with extended structures has become an important and fundamental topic in chemistry. To systematically control the chirality of novel organic-inorganic frameworks, histidinium-based cationic structure-directing agents containing specific chiral information are introduced. In this way, two chiral compounds, [(l-hisH )MoO F ] ⋅H O (L) and [(d-hisH )MoO F ] ⋅H O (D), and an achiral oxyfluoride, (l/d-hisH )MoO F (LD) (his=histidine, C H N O ) have been successfully self-assembled by a slow evaporation method.

meso-Bis(ethynyl) Versus meso-Bis(aryl) Calix[4]pyrroles: Dimensionally Well-Modulated Receptors That Can Regulate the Anion Binding Domains.

meso-Substituted calix[4]pyrroles 2-6 containing a direct meso-ethynyl linker displayed high binding affinities and unique conformational features on halide anion binding. A general conformational bias for the equatorial alignments of the meso-(aryl)ethynyl groups was observed in the host-halide complexes which was attributed to the repulsive anion-alkyne interactions and released steric strain. Such conformational features of host-halide complexes persisted even in the case of calix[4]pyrrole 6 bearing cationic meso components, which displayed the highest binding affinity for chloride anions among known meso-aryl calix[4]pyrroles.

Trapping of Stable [4n+1] π-Electron Species from Peripherally Substituted, Conformationally Rigid, Antiaromatic Hexaphyrins.

Peripherally substituted antiaromatic naphthorosarins have been synthesized for the first time. The synthesis was accomplished by acid-catalyzed condensation of naphthobipyrrole building blocks with aromatic aldehydes. The naphthobipyrrole building blocks were synthesized by simple oxidative coupling of the corresponding pyrrole substituted aromatics.

Layered Bismuth Oxyfluoride Nitrates Revealing Large Second-Harmonic Generation and Photocatalytic Properties.

Two novel bismuth oxyfluoride nitrates, BiOF(NO) and BiOF(NO), have been synthesized via hydrothermal reactions. Whereas BiOF(NO) crystallizes in the centrosymmetric (CS) hexagonal space group, P6/ m, BiOF(NO) crystallizes in the polar noncentrosymmetric (NCS) trigonal space group, R3. The backbones of the title compounds reveal double layered structures composed of asymmetric BiF(O/F) or BiOF polyhedra and NO trigonal planar groups.

CsVO(O)CO: an exceptionally thermostable carbonatoperoxovanadate with an extremely large second-harmonic generation response.

A novel nonlinear optical (NLO) carbonatoperoxovanadate, CsVO(O)CO, with an exceptionally high thermostability was successfully synthesized by introducing highly polarizable Cs cations and inorganic polydentate carbonate anions into asymmetric peroxovanadates. The structure of CsVO(O)CO is composed of distorted [VO(O)CO] units and charge balancing Cs cations. The title compound exhibits the largest NLO intensity ever found in the current carbonate NLO materials, e.

Unexpected halide anion binding modes in meso-bis-ethynyl picket-calix[4]pyrroles: effects of meso-π (ethynyl) extension.

meso-Ethynyl extended aryl-picket calix[4]pyrroles 2 and 3 are designed and synthesized by directly anchoring arylethynyl groups at diametrically opposed meso-positions. The critical roles of direct ethynyl linkers are manifested through the isolation of unexpected host-anion conformers of meso-arylethynyl calix[4]pyrroles and a significant enhancement in halide binding affinities.

Variable Asymmetric Chains in Transition Metal Oxyfluorides: Structure-Second-Harmonic-Generation Property Relationships.

Four novel transition metal oxyfluorides, [Zn(pz)][MoOF]·0.1HO (1), [Zn(pz)F][Zn(pz)][WOF] (2), [Cd(pz)][Cd(pz)(HO)][MoOF]·0.625HO (3), and [Zn(mpz)][MoOF] (4) (pz = pyrazole; mpz = 3-methyl pyrazole) have been synthesized.

Rb VO(O ) CO : A Four-in-One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second-Harmonic Generation Response.

A nonlinear optical (NLO) carbonatoperoxovanadate, Rb VO(O ) CO , was synthesized through a simple solution-evaporation method in phase-pure form. Single-crystal X-ray diffraction revealed that the structure of Rb VO(O ) CO consists of important noncentrosymmetric (NCS) chromophores, that is, π-delocalized (CO ) groups, a second-order Jahn-Teller (SOJT) distortive V cation, and π-localized distorted O groups, as well as charge-balancing polarizable Rb ions. The powder second-harmonic generation (SHG) measurements indicated that Rb VO(O ) CO is phase-matchable (Type I) and exhibits a remarkably strong SHG response circa 21.

LiM(SeO) (M = Co, Ni, and Cd) and LiZn(SeO): Selenites with Late Transition-Metal Cations.

A series of lithium metal selenites, LiM(SeO) (M = Co, Ni, and Cd) and LiZn(SeO), were synthesized by hydrothermal and solid-state reactions. LiM(SeO) is composed of Li cations, MO octahedra, and SeO polyhedra, while LiZn(SeO) consists of Li, Zn(Li)O tetrahedra, and SeO polyhedra. Isostructural LiCo(SeO) and LiNi(SeO) crystallize in the rhombohedral space group R3̅, forming a three-dimensional distorted cubic lattice.

Noncentrosymmetric (NCS) solid solutions: elucidating the structure-nonlinear optical (NLO) property relationship and beyond.

A systematic approach toward the discovering of novel functional noncentrosymmetric (NCS) materials revealing technologically useful applications is an ongoing challenge. This Frontiers article investigates a series of NCS solid solutions with respect to their crystal structure and second-harmonic generation (SHG) response. The solid solutions include NCS polar aluminoborates, AlGaBO (0.

Cationic Site-Preference in the YbCaAlSb (4.81 ≤ x ≤ 10.57) Series: Theoretical and Experimental Studies.

Four quaternary Zintl phases with mixed-cations in the YbCaAlSb (4.81 ≤ x ≤ 10.57) series have been synthesized by using the arc-melting and the Sn metal-flux reaction methods, and the isotypic crystal structures of the title compounds have been characterized by both powder and single-crystal X-ray diffraction (PXRD and SXRD) analyses.

LiMn(SeO): Lithium-Rich Transition Metal Selenite Containing Jahn-Teller Distortive Cations.

A novel lithium-rich transition metal selenite, LiMn(SeO), that is composed of a Jahn-Teller distortive cation, Mn, in the high spin d state, and a second-order Jahn-Teller (SOJT) distortive lone pair cation, Se, has been synthesized via hydrothermal and high temperature solid state reactions. The selenite is classified as a molecular compound consisting of MnO octahedra, SeO trigonal pyramids, and Li cations. Considering the Li-O interactions, the structure of LiMn(SeO) may be described as a pseudo-three-dimensional framework as well.

Photoconversion Mechanisms and the Origin of Second-Harmonic Generation in Metal Iodates with Wide Transparency, NaLn(IO) (Ln = La, Ce, Sm, and Eu) and NaLa(IO):Ln (Ln = Sm and Eu).

Four new metal iodates, namely, NaLn(IO) (Ln = La, Ce, Sm, and Eu), and a series of NaLa(IO):Ln (Ln = Sm and Eu) solid solutions were synthesized through hydrothermal reactions. The structures of the title compounds are similar to that of NaY(IO) crystallizing in the acentric monoclinic space group Cc. The iodate materials reveal layered structures composed of LnO square antiprisms and IO polyhedra, in which each layer is connected by the I···O interactions.