Crystal Growth and Crystal Structures of Gold(V) Compounds: Cu(AuF6)2, Ag(AuF6)2, and O2(CuF)3(AuF6)4 ⋅ HF

Crystal growth from anhydrous hydrogen fluoride solutions of M²⁺ (M=Cu, Ag) and [AuF₆]⁻ gave M(AuF₆)₂ salts (M=Cu, Ag). Similar attempts to prepare single crystals of the corresponding nickel, zinc and magnesium salts failed. The crystal structure of Cu(AuF₆)₂ consists of layers of Cu²⁺ cations connected by [AuF₆]⁻ anions, thus forming slabs. Only van der Waals interactions exist between adjacent slabs. The crystal structure of Ag(AuF₆)₂ consists of a three-dimensional framework in which Ag⁺ cations are linked by [AuF₆]⁻ anions. Both structures are members of the M^II(X^VF₆)₂ family, in which seven different structure types have been observed to date. In the crystal structure of O₂(CuF)₃(AuF₆)₄ ⋅ HF, the bridging AuF₆ units connect [−Cu−F−Cu−F−]_∞ chains to form stacks between which O₂⁺ cations and HF molecules are located.     

Solid Contact Ion-selective Electrodes on Printed Circuit Board with Membrane Displacement

Multiplexed solid-contact ion-selective electrodes (SCISEs) are fabricated using printed circuit board (PCB) and mesoporous carbon black (MCB) as ion-to-electron transducer (solid contact). Four sensor configurations were examined and showed that in addition to MCB, the sensor configuration plays crucial role in the stability of the potential response. The enhanced sensor stability was also linked with suppression of transmembrane flux of water. The sensors exhibited near-Nernstian sensitivity (58.1 mV/dec for K⁺ ISEs and −55.1 mV/dec for NO₃^- ISEs), low detection limits (1.5–2.2 μM), and good short-term stability (∼0.1 mV/min). Sensors can be stored dry and used without preconditioning. This work demonstrates a promising approach to combining PCB technology and carbon black for large-scale production of low cost ISEs for point-of-care testing, wearables, or in situ field measurements.     

The Universal Super Cation-Conductivity in Multiple-cation Mixed Chloride Solid-State Electrolytes

As exciting candidates for next-generation energy storage, all-solid-state lithium batteries (ASSLBs) are highly dependent on advanced solid-state electrolytes (SSEs). Here, using cost-effective LaCl₃ and CeCl₃ lattice (UCl₃-type structure) as the host and further combined with a multiple-cation mixed strategy, we report a series of UCl₃-type SSEs with high room-temperature ionic conductivities over 10⁻³ S cm⁻¹ and good compatibility with high-voltage oxide cathodes. The intrinsic large-size hexagonal one-dimensional channels and highly disordered amorphous phase induced by multi-metal cation species are believed to trigger fast multiple ionic conductions of Li⁺, Na⁺, K⁺, Cu⁺, and Ag⁺. The UCl₃-type SSEs enable a stable prototype ASSLB capable of over 3000 cycles and high reversibility at −30 °C. Further exploration of the brand-new multiple-cation mixed chlorides is likely to lead to the development of advanced halide SSEs suitable for ASSLBs with high energy density.     

Mixed-Valence BN-Doped Corannulene Trimer Radical Cations

Mixed-valence (MV) dimers have been extensively investigated, however, the structure and properties of purely organic MV trimers based on open-shell polycyclic aromatic hydrocarbons remain elusive. Herein, unprecedented MV BN-doped corannulene radical cations [ BN-Cor1 ]₃⋅⋅²⁺ ⋅ 2[BAryl^F₄]⁻ and [ BN-Cor2 ]₃⋅⋅²⁺ ⋅ 2[BAryl^F₄]⁻ were synthesized via chemical oxidation, and their structures were unambiguously confirmed by single-crystal X-ray diffraction. These uncommon radical cations consist of three corannulene cores and two [BAryl^F₄]⁻ anions, and three corannulene motifs [ BN-Cor1 ]₃⋅⋅²⁺ and [ BN-Cor2 ]₃⋅⋅²⁺ in the unit cell exhibit a trimer structure with a slipped π-stacking configuration. Detailed structural analyses further revealed that the corannulene cores exhibit an infinite layered self-assembly configuration, allowing their potential applications as building blocks for molecular conductors. The detection of a forbidden transition (Δm_s=±2) by electron paramagnetic resonance (EPR) spectroscopy further confirmed the existence of two unpaired electrons in the π-trimers and the MV characteristic of these two species. Variable-temperature EPR and conductivity measurements suggested that the BN-doped π-trimers exhibited antiferromagnetic coupling and conductivity properties.     

Charge-Transfer and Spin-Flip States: Thriving as Complements

Transition metal complexes with photoactive charge-transfer excited states are pervasive throughout the literature. In particular, [Ru(bpy)₃]²⁺ (bpy=2,2′-bipyridine), with its metal-to-ligand charge-transfer emission, has been established as a key complex. Meanwhile, interest in so-called spin-flip metal-centered states has risen dramatically after the molecular ruby [Cr(ddpd)₂]³⁺ (ddpd=N,N′-dimethyl-N,N′-dipyridin-2-yl-pyridine-2,6-diamine) led to design principles to access strong, long-lived emission from photostable chromium(III) complexes. This Review contrasts the properties of emissive charge-transfer and spin-flip states by using [Ru(bpy)₃]²⁺ and [Cr(ddpd)₂]³⁺ as prototypical examples. We discuss the relevant excited states, the tunability of their energy and lifetimes, and their response to external stimuli. Finally, we identify strengths and weaknesses of charge-transfer and spin-flip states in applications such as photocatalysis and circularly polarized luminescence.     

Two-Dimensional Supramolecular Polymerization of a Bis-Urea Macrocycle into a Brick-Like Hydrogen-Bonded Network

We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl₃ or tetrachloroethane, leading to 2D hydrogen-bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick-like hydrogen bonding pattern between bis-urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non-covalent interaction motif, which is of great interest for materials development.     

Understanding Conformational Properties and Role of Hydrogen Bonds in Glycosaminoglycans-Interleukin8 Complexes in Aqueous Medium by Molecular Dynamics Simulation

Atomistic molecular dynamics simulations were performed under ambient conditions to explore the conformational features and binding affinities of hexameric glycosaminoglycans (GAGs) with chemokine Interleukin8 (IL8) in an aqueous medium. We tried to understand the role of hydrogen bonds (HBs) involving conserved water in mediating the interactions. The Luzar-Chandler model was adopted to study the kinetics of HB breaking and formation concerning different water-mediated HBs. The conformational flexibilities of bound GAGs are due to the flexible glycosidic linkages than the occasional/rare ring pucker conformation. The free energy landscape constructed with ϕ, and ψ, depicted that different conformational minima associated with the glycosidic linkage flexibility of the GAGs in bound states are separated by energy barriers. The binding affinities of IL8 towards GAGs are favored through the electrostatic and non-polar solvation interactions. 4-different types of conserved water were explored in the solvent-mediated binding of GAGs with IL8. The average lifetime of the IL8-GAG direct HB pairs was ∼ten times less than the IL8-GAG-shared water HBs. This is due to the rapid establishment of HB breaking and reformation kinetics involving water of a shared layer. We find that despite the highly negatively charged surface of GAGs, the IL8 surface populated by non-cationic amino acids could serve as a promising binding site in addition to the cationic surface of the protein.     

A Series of Low-Coordinate Iron Selenido Complexes: Reactivity of a Linear Iron(I) Silylamide towards Selenium

A variety of different low-coordinate iron selenide complexes is reported. These are obtained by reaction of the linear iron(I) silylamide K{18c6}[Fe(N(Dipp)SiMe₃)₂] (Dipp=2,6-diisopropylphenyl) with red selenium. Careful adjustment of the reaction conditions results in the formation of unique low-coordinate selenido iron complexes, namely a monoselenide bridged [2Fe−1Se]²⁺ complex, as well as mononuclear iron per- and triselenides. Further, C−H bond activation of one of the silylamide ligands by a putative terminal iron monoselenide is observed.     

1,3-Sulfinate Migration Triggered by α-Imino Carbene and Divergent Zwitterion Cyclization: Synthesis of Cyclopropane,Dihydropyrrole, and Azepane Ring Systems

Cyclopropane, dihydropyrrole, and azepane ring systems were synthesized conveniently from sulfinate-tethered triazoles. The divergent synthetic strategy started with the unique 1,3-sulfinate migration of an α-imino carbene. The efficient reaction allowed control of the zwitterion bearing multiple reactive sites depending on the increased stability of the resulting carbocation and anion. The sulfinate was converted to a sulfone after the group migration, and a stable anion bearing two electron-withdrawing groups was thus formed. Catalytic amounts of iodide acted as a switch for the synthesis of cyclopropanes and dihydropyrroles. The reaction merits including readily available substrates, mild reaction conditions, and excellent functional group compatibility qualified this protocol a possible synthetic tool for cyclic compounds, especially for N-heterocycles.     

Synthetic K+ Channels Constructed by Rebuilding the Core Modules of Natural K+ Channels in an Artificial System

Different types of natural K⁺ channels share similar core modules and cation permeability characteristics. In this study, we have developed novel artificial K⁺ channels by rebuilding the core modules of natural K⁺ channels in artificial systems. All the channels displayed high selectivity for K⁺ over Na⁺ and exhibited a selectivity sequence of K⁺≈Rb⁺ during the transport process, which is highly consistent with the cation permeability characteristics of natural K⁺ channels. More importantly, these artificial channels could be efficiently inserted into cell membranes and mediate the transmembrane transport of K⁺, disrupting the cellular K⁺ homeostasis and eventually triggering the apoptosis of cells. These findings demonstrate that, by rebuilding the core modules of natural K⁺ channels in artificial systems, the structures, transport behaviors, and physiological functions of natural K⁺ channels can be mimicked in synthetic channels.