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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Inorganic Chemistry".

Deadline for manuscript submissions: closed (30 June 2021) | Viewed by 31365

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Prof. Dr. Nikolay I. Leonyuk

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Department of Crystallography and Crystal Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia
Interests: crystal growth; crystallography; crystal chemistry; crystal morphology; liquid phase epitaxy; micro- and nanocrystallization; inorganic compounds
* Passed away in May 2020
Special Issues, Collections and Topics in MDPI journals

Dr. Victor V. Mal'tsev

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Head of Crystallography&Crystal Growth Laboratory, Geological Faculty, Lomonosov Moscow State University, Moscow, Russia
Interests: single crystal growth and characterization of functional optical, laser, superconducting and magnetic crystal materials

Special Issue Information

Dear Colleagues,

There are numerous structural types of technologically promising inorganic materials, including complex silicates, germanates, phosphates, vanadates, borates, and oxides, which could be obtained in different crystalline forms: from bulk single crystals to low-dimensional structures. A problem which awaits further clarification concerns the nature of phase formation in these complex systems, considering this process from the viewpoint of crystal chemistry.

Generally, the structural stability of many silicates, phosphates, and germanates depends on the delocalization of formal charges of the A_nO_m (A = Si,Ge,P) anions as a result of their polycondensation. It is intensified with decreasing valence and increasing size of cations and accompanied by delocalization and the decrease of anion formal charge. The regular variations in their structural motives makes it possible to forecast new phase systems for the synthesis of highly efficient laser, piezo-, acoustoelectric, magnetic, and other many promising multifunctional materials which have still not been synthesized, and many more whose crystals are not available in good size or quality. On the other hand, investigation of these inorganic structures sets forth judicious ways towards a better understanding of their formation mechanisms.

The Special Issue suggested is intended to fill in a gap in this field.

Prof. Dr. Nikolay I Leonyuk
Dr. Victor V. Mal'tsev
Guest Editors

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Keywords

Crystal growth
Crystallography
Crystal chemistry
Inorganic crystals
Multifunctional materials

Published Papers (12 papers)

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Research

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18 pages, 4695 KiB

Open AccessArticle

Biofilm Medium Chemistry and Calcium Oxalate Morphogenesis

by Aleksei Rusakov, Maria Kuz’mina and Olga Frank-Kamenetskaya

Molecules 2021, 26(16), 5030; https://doi.org/10.3390/molecules26165030 - 19 Aug 2021

Cited by 5 | Viewed by 1866

Abstract

The present study is focused on the effect of biofilm medium chemistry on oxalate crystallization and contributes to the study of the patterns of microbial biomineralization and the development of nature-like technologies, using the metabolism of microscopic fungi. Calcium oxalates (weddellite and whewellite in different ratios) were synthesized by chemical precipitation in a weakly acidic environment (pH = 4–6), as is typical for the stationary phase of micromycetes growth, with a ratio of Ca²⁺/C₂O₄²⁻ = 4.0–5.5, at room temperature. Additives, which are common for biofilms on the surface of stone in an urban environment (citric, malic, succinic and fumaric acids; and K⁺, Mg²⁺, Fe³⁺, Sr²⁺, SO₄²⁺, PO₄³⁺ and CO₃²⁺ ions), were added to the solutions. The resulting precipitates were studied via X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDXS). It was revealed that organic acids, excreted by micromicetes, and some environmental ions, as well as their combinations, significantly affect the weddellite/whewellite ratio and the morphology of their phases (including the appearance of tetragonal prism faces of weddellite). The strongest unique effect leading to intensive crystallization of weddellite was only caused by the presence of citric acid additive in the medium. Minor changes in the composition of the additive components can lead to significant changes in the weddellite/whewellite ratio. The effect of the combination of additives on this ratio does not obey the law of additivity. The content of weddellite in the systems containing a representative set of both organic acids and environmental ions is ~20 wt%, which is in good agreement with natural systems. Full article

(This article belongs to the Special Issue Crystallography and Crystal Chemistry)

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13 pages, 2094 KiB

Open AccessArticle

The Solvent Effect on Composition and Dimensionality of Mercury(II) Complexes with Picolinic Acid

by Željka Soldin, Boris-Marko Kukovec, Dubravka Matković-Čalogović and Zora Popović

Molecules 2021, 26(16), 5002; https://doi.org/10.3390/molecules26165002 - 18 Aug 2021

Cited by 2 | Viewed by 1978

Abstract

Three new mercury(II) coordination compounds, {[HgCl(pic)]}_n (1), [HgCl(pic)(picH)] (2), and [HgBr(pic)(picH)] (3) (picH = pyridine-2-carboxylic acid, picolinic acid) were prepared by reactions of the corresponding mercury(II) halides and picolinic acid in an aqueous (1) or alcohol–methanol or ethanol (2 and 3) solutions. Two different types of coordination compounds were obtained depending on the solvent used. The crystal structures were determined by the single-crystal X-ray structural analysis. Compound 1 is a one-dimensional (1-D) coordination polymer with mercury(II) ions bridged by chelating and bridging N,O,O′-picolinate ions. Each mercury(II) ion is four-coordinated with a bidentate picolinate ion, a carboxylate O atom from the symmetry-related picolinate ion and with a chloride ion; the resulting coordination environment can be described as a highly distorted tetrahedron. Compounds 2 and 3 are isostructural mononuclear coordination compounds, each mercury(II) ion being coordinated with the respective halide ion, N,O-bidentate picolinate ion, and N,O-bidentate picolinic acid in a highly distorted square-pyramidal coordination environment. Compounds 1–3 were characterized by IR spectroscopy, PXRD, and thermal methods (TGA/DSC) in the solid state and by ¹H and ¹³C NMR spectroscopy in the DMSO solution. Full article

(This article belongs to the Special Issue Crystallography and Crystal Chemistry)

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12 pages, 1912 KiB

Open AccessArticle

Weak Intermolecular Interactions in a Series of Bioactive Oxazoles

by Anita M. Grześkiewicz, Tomasz Stefański and Maciej Kubicki

Molecules 2021, 26(10), 3024; https://doi.org/10.3390/molecules26103024 - 19 May 2021

Cited by 2 | Viewed by 1723

Abstract

The intermolecular interactions in a series of nine similar 4,5-phenyl-oxazoles were studied on the basis of crystal structures determined by X-ray diffraction. The crystal architectures were analyzed for the importance and hierarchies of different, weak intermolecular interactions using three approaches: the geometrical characteristics, topological analysis (for the model based on the transfer of multipolar parameters), and energetics of the molecule–molecule interactions. The geometries of the molecules were quite similar and close to the typical values. The results of the analysis of the interactions suggest that the number of nonspecific interactions is more important than the apparent strength of the specific interactions. The interactions involving covalently bound bromine and divalent sulfur atoms were classified as secondary, they certainly did not define the crystal packing, and they played a minor role in the overall crystal cohesion energies. Incidentally, another method for confirming the degree of isostructurality, according to the topologies of the interactions, is described. Full article

(This article belongs to the Special Issue Crystallography and Crystal Chemistry)

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16 pages, 14426 KiB

Open AccessArticle

Magnetic ZnO Crystal Nanoparticle Growth on Reduced Graphene Oxide for Enhanced Photocatalytic Performance under Visible Light Irradiation

by Rania Elshypany, Hanaa Selim, K. Zakaria, Ahmed H. Moustafa, Sadeek A. Sadeek, S.I. Sharaa, Patrice Raynaud and Amr A. Nada

Molecules 2021, 26(8), 2269; https://doi.org/10.3390/molecules26082269 - 14 Apr 2021

Cited by 25 | Viewed by 2294

Abstract

Magnetite zinc oxide (MZ) (Fe₃O₄/ZnO) with different ratios of reduced graphene oxide (rGO) was synthesized using the solid-state method. The structural and optical properties of the nanocomposites were analyzed using transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, Fourier-transform infrared spectroscopy (FTIR), ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis/DRS), and photoluminescence (PL) spectrophotometry. In particular, the analyses show higher photocatalytic movement for crystalline nanocomposite (MZG) than MZ and ZnO nanoparticles. The photocatalytic degradation of methylene blue (MB) with crystalline ZnO for 1.5 h under visible light was 12%. By contrast, the photocatalytic activity for MZG was more than 98.5%. The superior photocatalytic activity of the crystalline nanocomposite was detected to be due to the synergistic effect between magnetite and zinc oxide in the presence of reduced graphene oxide. Moreover, the fabricated nanocomposite had high electron–hole stability. The crystalline nanocomposite was stable when the material was used several times. Full article

(This article belongs to the Special Issue Crystallography and Crystal Chemistry)

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12 pages, 2858 KiB

Open AccessArticle

Expanding the Averievite Family, (MX)Cu₅O₂(T⁵⁺O₄)₂ (T⁵⁺ = P, V; M = K, Rb, Cs, Cu; X = Cl, Br): Synthesis and Single-Crystal X-ray Diffraction Study

by Ilya V. Kornyakov, Victoria A. Vladimirova, Oleg I. Siidra and Sergey V. Krivovichev

Molecules 2021, 26(7), 1833; https://doi.org/10.3390/molecules26071833 - 24 Mar 2021

Cited by 9 | Viewed by 2154

Abstract

Averievite-type compounds with the general formula (MX)[Cu₅O₂(TO₄)], where M = alkali metal, X = halogen and T = P, V, have been synthesized by crystallization from gases and structurally characterized for six different compositions: 1 (M = Cs; X = Cl; T = P), 2 (M = Cs; X = Cl; T = V), 3 (M = Rb; X = Cl; T = P), 4 (M = K; X = Br; T = P), 5 (M = K; X = Cl; T = P) and 6 (M = Cu; X = Cl; T = V). The crystal structures of the compounds are based upon the same structural unit, the layer consisting of a kagome lattice of Cu²⁺ ions and are composed from corner-sharing (OCu₄) anion-centered tetrahedra. Each tetrahedron shares common corners with three neighboring tetrahedra, forming hexagonal rings, linked into the two-dimensional [O₂Cu₅]⁶⁺ sheets parallel to (001). The layers are interlinked by (T⁵⁺O₄) tetrahedra (T⁵⁺ = V, P) attached to the bases of the oxocentered tetrahedra in a “face-to-face” manner. The resulting electroneutral 3D framework {[O₂Cu₅](T⁵⁺O₄)₂}⁰ possesses channels occupied by monovalent metal cations M⁺ and halide ions X⁻. The halide ions are located at the centers of the hexagonal rings of the kagome nets, whereas the metal cations are in the interlayer space. There are at least four different structure types of the averievite-type compounds: the P-3m1 archetype, the 2 × 2 × 1 superstructure with the P-3 space group, the monoclinically distorted 1 × 1 × 2 superstructure with the C2/c symmetry and the low-temperature P2₁/c superstructure with a doubled unit cell relative to the high-temperature archetype. The formation of a particular structure type is controlled by the interplay of the chemical composition and temperature. Changing the chemical composition may lead to modification of the structure type, which opens up the possibility to tune the geometrical parameters of the kagome net of Cu²⁺ ions. Full article

(This article belongs to the Special Issue Crystallography and Crystal Chemistry)

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13 pages, 4578 KiB

Open AccessArticle

Crystals at a Carrefour on the Way through the Phase Space: A Middle Path

by Yury V. Torubaev and Ivan V. Skabitsky

Molecules 2021, 26(6), 1583; https://doi.org/10.3390/molecules26061583 - 13 Mar 2021

Cited by 5 | Viewed by 1498

Abstract

Multiple supramolecular functionalities of cyclic α-alkoxy tellurium-trihalides (including Te---O, Te---X (X = Br, I) and Te---π(C=C) supramolecular synthons) afford rich crystal packing possibilities, which consequently results in polymorphism or Z’ > 1 crystal structures. Example of three crystal forms of cyclohexyl-ethoxy-tellurium-trihalides, one of which combines the packing of two others, affords a unique model to observe the supramolecular synthon evolution at the early stages of crystallization, when crystals on the way find themself at a carrefour between the evolutionally close routes, but fail to choose between two energetically close packing patterns, so taking the “middle path”, which incorporates both of them (and results in two crystallographically independent molecules). In general, this allows a better understanding of the existing structures, and an instrument to search for the new polymorphic forms. Full article

(This article belongs to the Special Issue Crystallography and Crystal Chemistry)

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14 pages, 6383 KiB

Open AccessArticle

GaPO₄ Single Crystals: Growth Condition by Hydrothermal Refluxing Method

by Denis Balitsky, Etienne Philippot, Vladimir Balitsky, Ludmila Balitskaya, Tatiana Setkova, Tatiana Bublikova and Philippe Papet

Molecules 2020, 25(19), 4518; https://doi.org/10.3390/molecules25194518 - 02 Oct 2020

Cited by 3 | Viewed by 2611

Abstract

Bulk GaPO₄ is an advanced piezoelectric material operating under high temperatures according to the α-β phase transition at 970 °C. This work presents the technological development of a hydrothermal refluxing method first applied for GaPO₄ single crystal growth. Crystals of 10–20 g were grown in mixtures of aqueous solutions of low- and high-vapor-pressure acids (H₃PO₄/HCl) at 180–240 °C (10–20 bars). The principal feature of the refluxing method is a spatial separation of crystal growth and nutrient dissolution zones. This leads to a constant mass transportation of the dissolved nutrient, even for materials with retrograde solubility. Mass transport is carried out by dissolution of GaPO₄ nutrient in a dropping flow of condensed low-vapor-pressure solvent. This method allows an exact saturation at temperature of equilibrium and avoids spontaneous crystallization as well loss of seeds. Grown crystals have a moderate OH⁻ content and reasonable structural uniformity. Moreover, the hydrothermal refluxing method allows a fine defining of GaPO₄ concentration in aqueous solutions of H₃PO₄, H₂SO₄, HCl and their mixtures at set T–P parameters (T < 250 °C, p = 10–30 bars). The proposed method is relatively simple to use, highly reproducible for crystal growth of GaPO₄ and probably could applied to other compounds with retrograde solubility. Full article

(This article belongs to the Special Issue Crystallography and Crystal Chemistry)

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15 pages, 5536 KiB

Open AccessArticle

Channel Waveguides in Lithium Niobate and Lithium Tantalate

by Yi Lu, Benjamin Johnston, Peter Dekker, Michael J. Withford and Judith M. Dawes

Molecules 2020, 25(17), 3925; https://doi.org/10.3390/molecules25173925 - 27 Aug 2020

Cited by 2 | Viewed by 3068

Abstract

Low-loss photonic waveguides in lithium niobate offer versatile functionality as nonlinear frequency converters, switches, and modulators for integrated optics. Combining the flexibility of laser processing with liquid phase epitaxy we have fabricated and characterized lithium niobate channel waveguides on lithium niobate and lithium tantalate. We used liquid phase epitaxy with K₂O flux on laser-machined lithium niobate and lithium tantalate substrates. The laser-driven rapid-prototyping technique can be programmed to give machined features of various sizes, and liquid phase epitaxy produces high quality single-crystal, lithium niobate channels. The surface roughness of the lithium niobate channels on a lithium tantalate substrate was measured to be 90 nm. The lithium niobate channel waveguides exhibit propagation losses of 0.26 ± 0.04 dB/mm at a wavelength of 633 nm. Second harmonic generation at 980 nm was demonstrated using the channel waveguides, indicating that these waveguides retain their nonlinear optical properties. Full article

(This article belongs to the Special Issue Crystallography and Crystal Chemistry)

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9 pages, 1330 KiB

Open AccessArticle

Laser-Inscribed Diamond Waveguide Resonantly Coupled to Diamond Microsphere

by Nurperi Yavuz, Mustafa Mert Bayer, Hüseyin Ozan Ҫirkinoğlu, Ali Serpengüzel, Thien Le Phu, Argyro Giakoumaki, Vibhav Bharadwaj, Roberta Ramponi and Shane M. Eaton

Molecules 2020, 25(11), 2698; https://doi.org/10.3390/molecules25112698 - 10 Jun 2020

Cited by 3 | Viewed by 2735

Abstract

An all-diamond photonic circuit was implemented by integrating a diamond microsphere with a femtosecond-laser-written bulk diamond waveguide. The near surface waveguide was fabricated by exploiting the Type II fabrication method to achieve stress-induced waveguiding. Transverse electrically and transverse magnetically polarized light from a tunable laser operating in the near-infrared region was injected into the diamond waveguide, which when coupled to the diamond microsphere showed whispering-gallery modes with a spacing of 0.33 nm and high-quality factors of 10⁵. By carefully engineering these high-quality factor resonances, and further exploiting the properties of existing nitrogen-vacancy centers in diamond microspheres and diamond waveguides in such configurations, it should be possible to realize filtering, sensing and nonlinear optical applications in integrated diamond photonics. Full article

(This article belongs to the Special Issue Crystallography and Crystal Chemistry)

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20 pages, 4017 KiB

Open AccessReview

Layered Cuprates Containing Flat Fragments: High-Pressure Synthesis, Crystal Structures and Superconducting Properties

by Evgeny M. Kopnin

Molecules 2021, 26(7), 1862; https://doi.org/10.3390/molecules26071862 - 25 Mar 2021

Cited by 5 | Viewed by 2536

Abstract

High-pressure synthesis and crystal structures of the homologous series AuBa₂(Ca,Ln)_n−1Cu_nO_2n+3 (n = 1–4; Ln = rare-earth cations) are described. Their crystal structures and superconducting properties are compared with the corresponding members of the Hg-homologous series. Numerous cuprates containing flat structural fragments (CuO₄, CO₃ and BO₃) synthesized mainly at high pressure are compared in terms of structural peculiarities and superconducting properties. Importance and future prospects of high-pressure application for the preparation of new superconducting oxides are discussed. Full article

(This article belongs to the Special Issue Crystallography and Crystal Chemistry)

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50 pages, 6084 KiB

Open AccessReview

Peculiar Structural Effects in Pure and Doped Functional Single Crystals of Complex Compositions

by Galina Kuz’micheva and Irina Kaurova

Molecules 2020, 25(10), 2451; https://doi.org/10.3390/molecules25102451 - 25 May 2020

Cited by 5 | Viewed by 3806

Abstract

Results of a detailed structural characterization of nominally pure and doped single crystals of scheelite, eulytin, and perovskite families obtained by melt methods were considered and analyzed. The influence of growth and post-growth annealing conditions on actual compositions of crystals is shown. The reasons for the coloration of the crystals are explained. A change in crystal symmetry due to crystal–chemical and growth reasons is considered. The use of structural analysis and X-ray absorption spectroscopy is substantiated to reveal the role of activator ions in the formation of statistical and local structures, respectively. A relationship between the distribution of activator ions over crystallographic sites and photoluminescent parameters of materials is established, which allows selecting optimal systems for the application. The combined results of studying single-crystal compounds of other classes (huntite, sillenite, whitlockite, garnet, tetragonal bronzes) allow formulating and summarizing structural effects that appeared in the systems and caused by various factors and, in many cases, due to the local environment of cations. A principal difference in the structural behavior of solid solutions and doped compounds is shown. The methodology developed for single-crystal samples of complex compositions can be recommended for the systematic structural studies of functional materials of different compositions. Full article

(This article belongs to the Special Issue Crystallography and Crystal Chemistry)

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26 pages, 3317 KiB

Open AccessReview

Crystal Chemistry of High-Temperature Borates

by Nikolay I. Leonyuk, Victor V. Maltsev and Elena A. Volkova

Molecules 2020, 25(10), 2450; https://doi.org/10.3390/molecules25102450 - 25 May 2020

Cited by 14 | Viewed by 4121

Abstract

In recent years borate-based crystals has attracted substantial interest among the research community. The overall importance of this family of materials is reflected in miscellaneous articles and several reviews that have been published over the years. Crystalline borate materials exhibit numerous interesting physical properties, which make them promising for further practical applications. Diversity of functional characteristics results from their high structural flexibility caused in the linkage of planar/non–planar BO₃ groups and BO₄ tetrahedra, which can occur as isolated or condensed structural units. This report is a brief review on crystal chemistry and structure features of anhydrous/high-temperature borates. Polymorphism of boron-oxygen radicals has been considered basing on cations’ nature and synthesis conditions. Analysis of the laws governing borates structures and general principles of their systematics was discussed. As a result, an alternative classification of anhydrous compounds has been considered. It is based on four orders of their subdivision: (1) by the variety of anion formers, (2) by the cation charge, (3) by the N = N_M:N_B, i.e., ratio of metal atoms number to the ratio of boron atoms number (N-factor) value indicating the borate structural type (if it is known), (4) by the cation type and size. Full article

(This article belongs to the Special Issue Crystallography and Crystal Chemistry)

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