Size-Controlled Synthesis of Luminescent Few-Atom Silver Clusters via Electron Transfer in Isostructural Redox-Active Porous Ionic Crystals.

Ag clusters with a controlled number of atoms have received significant interest because they show size-dependent catalytic, optical, electronic, or magnetic properties. However, the synthesis of size-controlled, ligand-free, and air-stable Ag clusters with high yields has not been well-established. Herein, it is shown that isostructural porous ionic crystals (PICs) with redox-active polyoxometalates (POMs) can be used to synthesize Ag clusters via electron transfer from POMs to Ag+ . Ag clusters with average numbers of three, four, or six atoms emitting blue, green, or red colors, respectively, are formed and stabilized in the PICs under ambient conditions without any protecting ligands. The cluster size solely correlates with the degree of electron transfer, which is controlled by the reduction time and types of ions or elements of the PICs. Thus, advantages have been taken of POMs as electron sources and PICs as scaffolds to demonstrate a convenient method to obtain few-atom Ag clusters.

Structures and properties of ionic crystals and condensed phase ionic liquids predicted with the generalized energy-based fragmentation method.

The generalized energy-based fragmentation (GEBF) approach is extended to facilitate ab initio investigations of structures, lattice energies, vibrational spectra and 1 H NMR chemical shifts of ionic crystals and condensed-phase ionic liquids (ILs) with the periodic boundary conditions (PBC). For selected periodic systems, our results demonstrate that the so-called PBC-GEBF approach can provide satisfactory descriptions on ground-state energies, structures, and vibrational spectra of ionic crystals and IL crystals. The PBC-GEBF approach is then applied to three realistic condensed phase systems. For three ionic crystals (LiCl, NaCl, and KCl), we apply the PBC-GEBF approach with MP2 theory as well as some popular DFT methods to investigate their crystal structures and lattice energies. Our calculations indicate that the crystal structures obtained with PBC-GEBF-MP2/6-311 + G** are very close to the corresponding X-ray structures, while PBC-GEBF-ωB97X-D/6-311 + G** provides satisfactory prediction for crystal structures and lattice energies. For two polymorphs of [n-C4 mim][Cl] crystals, we find that the PBC-GEBF approach at the M06-2X/6-311 + G** level can give a satisfactory descriptions on structures and Raman spectra of these two crystals. Furthermore, for [C2 mim][BF4 ] ILs, we demonstrate that their 1 H NMR chemical shifts can be estimated from averaging over 5 typical snapshots (extracted from MD simulations) with the PBC-GEBF approach at the B97-2/pcSseg-2 level. The calculated results account for the observed experimental data quite well. Therefore, we expect that the PBC-GEBF approach, combined with various quantum chemistry methods, will become an effective tool in predicting structures and properties of ionic crystals and condensed-phase ILs.

Effect of Periodic Arrays of Defects on Lattice Energy Minimizers.

We consider interaction energies E f [ L ] between a point O ∈ R d , d ≥ 2 , and a lattice L containing O, where the interaction potential f is assumed to be radially symmetric and decaying sufficiently fast at infinity. We investigate the conservation of optimality results for E f when integer sublattices kL are removed (periodic arrays of vacancies) or substituted (periodic arrays of substitutional defects). We consider separately the non-shifted ( O ∈ k L ) and shifted ( O ∉ k L ) cases and we derive several general conditions ensuring the (non-)optimality of a universal optimizer among lattices for the new energy including defects. Furthermore, in the case of inverse power laws and Lennard-Jones-type potentials, we give necessary and sufficient conditions on non-shifted periodic vacancies or substitutional defects for the conservation of minimality results at fixed density. Different examples of applications are presented, including optimality results for the Kagome lattice and energy comparisons of certain ionic-like structures.

Long-Persistent Circularly Polarized Phosphorescence from Chiral Organic Ionic Crystals.

Long-persistent circularly polarized phosphorescence (LPCPP) is achieved for the first time in chiral organic ionic crystals at room temperature. The co-crystal composed of terephtalic acid (TPA) and chiral α-phenylethyamines (PEAs) gave rise to LPCPP with lifetimes up to 862 ms and large dissymmetric factor (glum ). The hybridization of TPA with chiral PEAs allows circular polarization of the generated long-persistent phosphorescence. The observed mirror-image twisted molecular structures in the rigid lattices were responsible for the chiroptical activation of the generated long-persistent phosphorescence.

Ultralong Phosphorescence from Organic Ionic Crystals under Ambient Conditions.

A new type of materials, organic salts in the crystal state, have ultralong organic phosphorescence (UOP) under ambient conditions. The change of cations (NH4+ , Na+ , or K+ ) in these phosphors gives access to tunable UOP colors ranging from sky blue to yellow green, along with ultralong emission lifetimes of over 504 ms. Single-crystal analysis reveals that unique ionic bonding can promote an ordered arrangement of organic salts in crystal state, which then can facilitate molecular aggregation for UOP generation. Additionally, reversible ultralong phosphorescence can be realized through the alternative employment of fuming gases (ammonia and hydrogen chloride), demonstrating its potential as a candidate for visual ammonic or hydrogen chloride gas sensing. The results provide an environmental responsible and practicable synthetic approach to expanding the scope of ultralong organic phosphorescent materials as well as their applications.

Dependence of Ion Transport on the Electronegativity of the Constituting Atoms in Ionic Crystals.

Ion transport in electrode and electrolyte materials is a key process in Li-based batteries. In this work, we study the mechanism and activation energy of ion transport (Ea ) in rock-salt Li-based LiX (X=Cl, Br, and I) materials. It is found that Ea at low external voltages, where Li-X Schottky pairs are the most favorable defect types, is about 0.42 times the Gibbs energy of formation of LiX compound (ΔGf ). The value of 0.42 is the slope of the electronegativity of anions of binary Li-based materials as a function of ΔGf . At high voltages, where the Fermi level is located very close to the valence band maximum (VBM), electrons can be excited from the VB to Li vacancy-induced states close to the Fermi level. Under this condition, the formation of Li vacancies that are compensated by holes is energetically more favorable than that of Li-X Schottky pairs, and therefore, the activation energies are lower in the former case. The wide range of reported experimental values of activation energies lies between calculated values at low and high voltage regimes. This work motivates further studies on the relation between the activation energy for ionic conductivity in solid materials and the intrinsic ground-state properties of their free atoms.

Probing Ionic Crystals by the Invariom Approach: An Electron Density Study of Guanidinium Chloride and Carbonate.

A comparative study of two guanidinium salts, chloride and carbonate, is carried out to test the performance of the invariom approach for ionic crystals. Although treating them as formed by isolated ions with no charge transfer between them, the invariom approach provides features of interionic contacts that are amazingly similar to those obtained from conventional charge density analysis of high-resolution X-ray diffraction data, thus emerging as an easy way towards reliable description of chemical bonding peculiarities in ionic crystals.

Solid State Ionics: from Michael Faraday to green energy-the European dimension.

Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag2S and PbF2 and coined terms such as cation and anion, electrode and electrolyte. In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an 'evolving scheme of materials science', point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987.

Further adventures of the perovskite family.

The perovskites are an intensely studied class of materials, with a breadth of possible compositions made even wider by the possibility of incorporating molecular ions. Here the context is discussed of a newly reported metal-free perovskite with the H3O+ ion on the B site.

Metal-free enantiomorphic perovskite [dabcoH2]2+[H3O]+Br- 3 and its one-dimensional polar polymorph.

The structure and stoichiometry of a new metal-free and ammonium-free compound [dabcoH2]2+H3O+Br- 3 (where [dabcoH2]2+ = 1,4-di-aza-bicyclo-[2.2.2]octane dication) correspond to the general formula ABX 3 characteristic of perovskites. In enantiomorphic trigonal polymorph α of [dabcoH2]2+H3O+Br- 3, the corner-sharing [H3O]Br6 octahedra combine into a 3D framework embedding [dabcoH2]2+ dications in pseudo-cubic cages. In the more dense polymorph ß, the face-sharing [H3O]Br6 octahedra form 1D polyanionic columns separated by [dabcoH2]2+ dications. These different topologies correlate with different crystal fields around the cations and their different disorder types: orientational disorders of [dabcoH2]2+ dications and H3O+ cations in polymorph α and positional disorder of [H3O]+ cations in polymorph ß. The orientational disorder increases the lengths of OH⋯Br hydrogen bonds in polymorph α, but NH⋯Br distances of ordered dabcoH2 dications are longer in polymorph ß. The presence of polar [H3O]+ cations in [dabcoH2]2+H3O+Br- 3 polymorphs offers additional polarizability of the centres compared with analogous metal-free [dabcoH2]2+[NH4]+Br- 3 perovskite.

Quadruple Anticounterfeiting Encryption: Anion-Modulated Forward and Reverse Excitation-Dependent Multicolor Afterglow in Two-Component Ionic Crystals.

Molecule-based afterglow materials with ultralong-lived excited states have attracted great attention owing to their unique applications in light-emitting devices, information storage, and anticounterfeiting. Herein, a series of new types of two-component ionic crystalline materials were fabricated by the self-assembly of cytosine and different anions under ambient conditions. The multiple intermolecular interactions of cytosine with phosphate and halogens anions can lead to abundant energy levels and different crystal stacking modes to control molecular aggregation and excited-state intermolecular proton transfer (ESIPT) process. Interestingly, H-aggregation-induced green to yellow room-temperature phosphorescence (RTP) and ESIPT-dominated cyan RTP to deep blue thermally activated delayed fluorescence (TADF) emission can be generated by tuning excitation wavelength, time evolution, and temperature. Furthermore, the combination of two-component ionic crystals can be used as multicolored candidates for quadruple information encryption. Therefore, this work not only develops an anion-modulated strategy to achieve color-tunable afterglow from both static and dynamic fashions but also provides a guideline for designing forward/reverse excitation-dependent luminescent materials.

Note on Crystallization for Alternating Particle Chains.

We investigate one-dimensional periodic chains of alternate type of particles interacting through mirror symmetric potentials. The optimality of the equidistant configuration at fixed density-also called crystallization-is shown in various settings. In particular, we prove the crystallization at any scale for neutral and non-neutral systems with inverse power laws interactions, including the three-dimensional Coulomb potential. We also show the minimality of the equidistant configuration at high density for systems involving inverse power laws and repulsion at the origin. Furthermore, we derive a necessary condition for crystallization at high density based on the positivity of the Fourier transform of the interaction potentials sum.

Multicomponent diffusion in ionic crystals: theoretical model and application to combined tracer- and interdiffusion in alkali feldspar.

We present a model for multicomponent diffusion in ionic crystals. The model accounts for vacancy-mediated diffusion on a sub-lattice and for diffusion due to binary exchange of different ionic species without involvement of vacancies on the same sub-lattice. The diffusive flux of a specific ionic species depends on the self-diffusion coefficients, on the diffusion coefficients related to the binary exchanges, and on the site fractions of all ionic species. The model delivers explicit expressions for these dependencies, which lead to a set of coupled non-linear diffusion equations. We applied the model to diffusion of 23 Na, 39 K, and 41 K in alkali feldspar. To this end, gem-quality crystals of alkali feldspar were used together with 41 K doped KCl salt as diffusion couples, which were annealed at temperatures between 800 ∘ and 950 ∘ C. Concentration-distance data for 23 Na, 39 K, and 41 K were obtained by Time of Flight Secondary Ion Mass Spectrometry. Over the entire investigated temperature range the Na self-diffusion coefficient is by a factor of ≥ 500 higher than the K self-diffusion coefficient. Diffusion mediated by binary 39 K- 41 K exchange is required for obtaining satisfactory fits of the model curves to the experimental data, and the respective kinetic coefficient is well constrained.

Conformational Transformations of (C12H25NH3(+))(Pyridinesulfonate) in the Solid State.

The phase-transition behaviors, crystal structures, and dielectric properties of four kinds of simple 1:1 organic salts of (C12H25NH3(+))(benzenesulfonate) and (C12 H25NH3(+))(pyridine sulfonates) were examined from the viewpoint of intermolecular hydrogen-bonding interactions and dynamic conformational transformation in molecular assemblies. Crystals of (C12H25NH3(+))(benzenesulfonate) and (C12H25NH3(+))(3-pyridinesulfonate) were isostructural and solid-solid and solid-liquid-crystal smectic A (SmA) phase transitions were observed. These two crystals formed rodlike cation-anion assemblies. However, the two salts, (C12H25NH3(+))(2-pyridinesulfonate) and (C12H25NH3(+))(4-pyridinesulfonate), formed largely bent L-shaped cation-anion conformations. Interesting conformational transformations from rodlike to L-shaped assemblies were observed in (C12H25NH3(+))(2-pyridinesulfonate) and (C12H25NH3(+))(3-pyridinesulfonate).

Electric Fields Produced in Cubic Crystals by Point Defects.

Charged point defects in crystals polarize the surrounding ions. These induced dipoles contribute to the electric field in the crystal. In this paper, lattice sums for the calculation of this contribution are given for the NaCl, CsCl, CaF2, and ZnS structures. Various positions for the defect are chosen, and the field evaluated near lattice sites in the vicinity of the defect, with radial (with respect to the defect) displacements of ± 20 percent of the cation-anion distance allowed away from each lattice site. The lattice sums are expressed in power series, including terms up to cubic in the displacements, and the coefficients tabulated.