Crystals Of Complex Research Articles

Pure‐Iodide Wide‐Bandgap Perovskites for High‐Efficiency Solar Cells by Crystallization Control

AbstractWide‐bandgap perovskite is a vital part of perovskite‐based tandem solar cells. Currently, wide‐bandgap perovskites are typically based on mixed‐halide (I/Br) materials, but suffer from photoinduced phase separation. The pure‐iodide formamidine/cesium (FA/Cs) based FAxCs1−xPbI3 perovskites with high Cs content are good candidates, whereas the control of crystallization is challenging due to the complex crystallization kinetics. Here, pure‐iodide FA0.5Cs0.5PbI3 wide‐bandgap perovskite solar cells is reported. As an acidic diammonium salt, methylenediaminium dichloride (MDACl2) is applied as an additive to control the whole crystallization process of perovskite films, including both nucleation and crystal growth. Starting from the solution chemistry, the MDACl2 additive with acidity and strong solvation properties can effectively regulate the chemical composition of perovskite precursor, thus inhibiting the growth of undesired 1D intermediates during the nucleation process. Besides, the incorporation of larger‐sized MDA2+ into the lattice compensates for the tolerance factor and accelerates the ion exchange reaction between FA+ and Cs+ in the crystal growth process. As a result, the crystallinity of the perovskite films is significantly improved, benefitting from the dual function of MDACl2. Finally, the efficiency of hole transport layer‐free carbon electrode‐based wide‐bandgap perovskite solar cells reaches 18.52%, which is the highest reported so far.

Toward Precision Deposition of Conductive Charge-Transfer Complex Crystals Using Nanoelectrochemistry.

The lack of understanding for precise synthesis and assembly of nano-entities remains a major challenge for nanofabrication. Electrocrystallization of a charge-transfer complex (CTC), tetrathiafulvalene bromide (TTF)Br, is studied on micro/nanoelectrodes for precision deposition of functional materials. The study reveals new insights into the entire CTC electrocrystallization process from the initial nanocluster nucleation to the final elongated crystals with hollow ends grown from the working electrode to the neighboring receiving electrode. On microelectrodes, the number of nucleation sites is reduced to one by lowering the applied overpotential or precursor concentration. Certain current-time transients exhibit significant induction periods prior to stable nucleus growth. The induction regime contains small fluctuating current spikes consistent with stochastic formation of precritical nanoclusters with lifetimes of 0.1-30s and sizes of 20-160nm. Electrochemical analyses further reveal rate, size distribution, and formation/dissipation dynamics of the nanoclusters. Crystal growth of (TTF)Br is further studied on triangular nanoelectrode patterns with thickness of 5-500nm, which shows a mass-transfer-controlled process applicable for precision deposition of functional (TTF)Br crystals. This study, for the first time, establishes CTC nanoelectrochemistry as a platform technology for precise deposition of conductive crystal assemblies spanning the source and drain electrode for sensing applications.

A Novel Approach to Analysis of Complex Crystallization Behavior in Zr-Based Bulk Metallic Glass by Non-isothermal Kinetics Studies

The complex crystallization behavior of the Zr40Ti15Cu10Ni10Be25 bulk metallic glass (BMG) produced by suction-casting method was studied with the non-isothermal DSC measurements with the heating rate from 5 to 40 K/min. Three exothermic phenomena were observed for the investigated material. The novel evaluation procedure for qualitative and quantitative analysis of intricate crystallization kinetics for Zr-based BMGs is proposed. The unusual deconvolution of the DSC curves based on a Gaussian function and a two-phase exponential decay function allowed for separate, detailed analysis of overlapped peaks. The activation energies for each crystallization stage were studied based on overall (Kissinger) and local (Kissinger–Akahira–Sunose) procedures. The KAS method applied separately for both low and high heating rates showed a significant difference in local activation energies. Finally, the local Avrami exponent evaluation revealed that the first two stages of crystallization are diffusion-controlled with mainly increasing nucleation rate, whereas the third crystallization is more growth-dominated.

Syntheses, Crystal Structure and Conducting Property of New 4-N,N-dimethyl benzyl-N-benzyl dithiocarbamato Cu(II) Complex

A new homoleptic copper (II) dithiocarbamate complex having molecular formula [Cu(C17 H19N2S2)2], has been synthesized and characterized by elemental analysis and spectroscopy (IR and UV–Vis). Single crystal X-ray studies confirm that the complex crystallises in monoclinic with space group P121/c1 and holding dimeric structure by weak Cu...S and H...H intractions. The existence of attractive intermolecular C−H⋯H−C interaction is a notable feature in the crystal packing of this complex. The electrical conductivity measurement between temperatures range of 303–393 K reflects that complex exhibits weak semiconducting behavior.

Unprecedented Coordination Compounds with 4,4′-Diaminodiphenylethane as a Supramolecular Agent and Ditopic Ligand: Synthesis, Crystal Structures and Hirshfeld Surface Analysis

In this pioneering research, mononuclear coordination complexes and coordination polymers were obtained using the conformationally flexible ditopic ligand 4,4′-diaminodiphenylethane and different metal salts (nitrates, sulfates, tetrafluoroborates and perchlorates). Seven new products, including the mononuclear complexes [Cd(2,2′-bpy)3](ClO4)2](dadpe)(4,4′-bpy) (1), [Ni(dadpe)2(H2O)4](SO4).H2O (2), one-dimensional coordination polymers {[Zn(NO3)(dadpe)(dmf)2](NO3)}n (3), {[Cd(2,2′-bpy)2(dadpe)](ClO4)2}n (4), and two-dimensional coordination polymers, {[Cd(4,4′-bpy)2(H2O)2](ClO4)2(dadpe)(EtOH)2}n (5), {[Co(4,4′-bpy)2(H2O)2](BF4)2(dadpe)(EtOH)2}n (6) and {[Cd(adi)(dadpe)](H2adi)}n (7), (dadpe=4,4′-diaminodiphenylethane, 2,2′-bpy=2,2′-bipyridine, 4,4′-bpy=4,4′-bipyridine, H2adi=adipic acid) were produced. The synthesized compounds were characterized by FTIR and single-crystal X-ray diffraction analyses. The dadpe was recorded as a neutral guest in the crystals of mononuclear complex 1 and in coordination polymers 5 and 6. In compound 2, two dadpe ligands coordinate in a monodentate mode and occupy two trans-positions in the [Ni(H2O)4(dadpe)2]2+ octahedral complex cation. Coordination polymers 3 and 4 represent single chains originating from dadpe as a bidentate linker in both. The H-donor’s possibilities of amino groups were utilized in the interconnection of coordination chains into H-bonded networks via NH(NH2)···O hydrogen bonds. The isostructural coordination polymers 5 and 6 comprise similar cationic square grids [M(4,4′-bpy)2(H2O)2]2+ [M=Cd (5), M=Co (6)], with sql topology balanced by the charge-compensated anions, while dadpe and EtOH as neutral guests are situated in the interlayer space. The neutral 2D coordination network in 7 with the sql topology originates from both adi and dadpe linkers as bidentate-bridging ligands, and the neutral H2adi is entrapped as a guest in crystal lattice. The impact of different types of intermolecular interactions was evaluated by Hirshfeld surface analysis.

Indomethacin: Effect of Diffusionless Crystal Growth on Thermal Stability during Long-Term Storage.

Differential scanning calorimetry and Raman spectroscopy were used to study the nonisothermal and isothermal crystallization behavior of amorphous indomethacin powders (with particle sizes ranging from 50 to 1000 µm) and their dependence on long-term storage conditions, either 0-100 days stored freely at laboratory ambient temperatures and humidity or placed in a desiccator at 10 °C. Whereas the γ-form polymorph always dominated, the accelerated formation of the α-form was observed in situations of heightened mobility (higher temperature and heating rate), increased amounts of mechanically induced defects, and prolonged free-surface nucleation. A complex crystallization behavior with two separated crystal growth modes (originating from either the mechanical defects or the free surface) was identified both isothermally and nonisothermally. The diffusionless glass-crystal (GC) crystal growth was found to proceed during the long-term storage at 10 °C and zero humidity, at the rate of ~100 µm of the γ-form surface crystalline layer being formed in 100 days. Storage at the laboratory temperature (still below the glass transition temperature) and humidity led only to a negligible/nondetectable GC growth for the fine indomethacin powders (particle size below ~150 µm), indicating a marked suppression of GC growth by the high density of mechanical defects under these conditions. The freely stored bulk material with no mechanical damage and a smooth surface exhibited zero traces of GC growth (as confirmed by microscopy) after >150 days of storage. The accuracy of the kinetic predictions of the indomethacin crystallization behavior was rather poor due to the combined influences of the mechanical defects, competing nucleation, and crystal growth processes of the two polymorphic phases as well as the GC growth complex dependence on the storage conditions within the vicinity of the glass transition temperature. Performing paired isothermal and nonisothermal kinetic measurements is thus highly recommended in macroscopic crystallization studies of drugs with similarly complicated crystal growth behaviors.

Phase transitions in complex functional liquid crystals—The entropy effect

Liquid crystal design and synthesis are being driven towards always more complexity. The self-assembly of poly- and shape-amphiphiles allow tailoring the soft material structures with double and even triple nanosegregation of functional building blocks. Alignment of the anisotropic liquid crystal is crucial, in order to generate a full control over the material’s function and performance. This procedure often needs an isotropic phase at accessible temperatures without decomposition. The impact of thermodynamic factors, such as cohesive energy density difference and entropy contributions, is discussed in this perspective paper using selected examples. In the process of molecular design such considerations can help to adjust transition temperatures and subsequently, to achieve aligned, complex liquid crystalline matter. This will allow access to new fields of liquid crystal applications.

Tweaking the Optoelectronic Properties of S-Doped Polycyclic Aromatic Hydrocarbons by Chemical Oxidation.

Peri-thiaxanthenothiaxanthene, an S-doped analog of peri-xanthenoxanthene, is used as a polycyclic aromatic hydrocarbon (PAH) scaffold to tune the molecular semiconductor properties by editing the oxidation state of the S-atoms. Chemical oxidation of peri-thiaxanthenothiaxanthene with H2 O2 led to the relevant sulfoxide and sulfone congeners, whereas electrooxidation gave access to sulfonium-type derivatives forming crystalline mixed valence (MV) complexes. These complexes depicted peculiar molecular and solid-state arrangements with face-to-face π-π stacking organization. Photophysical studies showed a widening of the optical bandgap upon progressive oxidation of the S-atoms, with the bis-sulfone derivative displaying the largest value (E00 =2.99 eV). While peri-thiaxanthenothiaxanthene showed reversible oxidation properties, the sulfoxide and sulfone derivatives mainly showed reductive events, corroborating their n-type properties. Electric measurements of single crystals of the MV complexes exhibited a semiconducting behavior with a remarkably high conductivity at room temperature (10-1 -10-2 S cm-1 and 10-2 -10-3 S cm-1 for the O and S derivatives, respectively), one of the highest reported so far. Finally, the electroluminescence properties of the complexes were tested in light-emitting electrochemical cells (LECs), obtaining the first S-doped mid-emitting PAH-based LECs.

Synthesis, crystal structure and properties of bis-(iso-seleno-cyanato-κN)tetra-kis-(pyridine-κN)nickel(II).

The reaction of nickel chloride hexa-hydrate with potassium seleno-cyanate and pyridine in water leads to the formation of crystals of the title complex, [Ni(NCSe)2(C5H5N)4], which were characterized by single-crystal X-ray diffraction. Its crystal structure consists of discrete complexes, located on centers of inversion, in which the Ni cations are sixfold coordinated by two terminal N-bonded seleno-cyanate anions and four pyridine ligands within a slightly distorted octa-hedral coordination. In the crystal, the complexes are connected by weak C-H⋯Se inter-actions. PXRD investigations revealed that a pure crystalline phase has formed. In the IR and Raman spectra, the C-N stretching vibrations are observed at 2083 and 2079 cm-1, respectively, in agreement with the presence of only terminally bonded anionic ligands. Upon heating, one well-resolved mass loss is observed, in which two of the four pyridine ligands are removed, leading to a compound with the composition Ni(NCSe)2(C5H5N)2. In this compound, the C-N stretching vibration is shifted to 2108 cm-1 (Raman) and 2115 cm-1 (IR), indicating the presence of μ-1,3-bridging anionic ligands. In its PXRD pattern, very broad reflections are observed, indicating for poor crystallinity and/or very small particle size. This crystalline phase is not isotypic to its Co and Fe analogs.

Effects of (Ba1/3Sb2/3)4+ on the structure and dielectric properties of Ce2Zr3(MoO4)9 ceramic at microwave frequency

The single-phase of Ce2[Zr1-x(Ba1/3Sb2/3)x]3(MoO4)9 (x = 0.01 ∼ 0.10) (CZBSxM) ceramics were synthesized by the classic solid-state route successfully. The influence of (Ba1/3Sb2/3)4+ replacement for Zr4+ on the lattice parameters, microstructure, chemical bonds and dielectric properties were discussed comprehensively. The X-ray diffraction (XRD) indicated that the CZBSxM ceramics are trigonal-type crystal structure with R-3c space group. The lattice parameters of CZBSxM ceramics were obtained via the Rietveld refinement method. The theory of complex crystals chemical bonds (P-V-L theory) was carried out to study the connections between the chemical bond and dielectric properties. The excellent dielectric properties (ɛr = 10.71, Q×f = 91,798 GHz and τf = −15.18 ppm/℃) were obtained at 700 ℃ in CZBS0.02M ceramic.

Reversible trans-to-cis photoisomerization and irreversible photocyclization reactions of a Co-coordinated stilbene derivative on chiral di-β-diketonate lanthanide complexes.

Six lanthanide complexes constructed from two chiral β-diketonates (d/l-fbc = 3-heptafluorobutyryl-(+)/(-)-camphorate), the stilbene derivative (E)-N',N'-bis(pyridin-2-ylmethyl)-4-styrylbenzoyl hydrazide (L), a trifluoroacetate anion (CF3CO2 -), and one water molecule, namely [Ln(d/l-fbc)2(L)(CF3CO2)]·H2O (LnC57H54F17N4O8, Ln = La (1, d-fbc), La (2, l-fbc), Sm (3, d-fbc), Eu (4, d-fbc), Eu (5, l-fbc), and Tb (6, d-fbc), were synthesized and characterized by single-crystal X-ray diffraction, 1H-NMR, elemental analysis, IR and UV-vis spectroscopy, and thermal gravimetric analysis. The photoisomerization reactions of these complexes were systematically studied by means of experimental and theoretical calculations. Crystals of complexes 1, 2, 3, and 4 were obtained and belong to the monoclinic crystal system and the C2 chiral space group. The Λ- and Δ-diastereomers coexist in their crystals and no apparent bisignate couplets are observed in their ECD spectra. Among the complexes, the photocyclization reaction is followed by the trans-to-cis photoisomerization reaction and competes with the trans-to-cis photoisomerization, then the photocyclization reaction continues. The photocyclization reaction is irreversible in this stilbene derivative and is delayed in the lanthanide complexes. These results provide a viable strategy for the design of promising new stilbene-attached dual-functional lanthanide-based optical-switching materials.

Rapid single crystal growth via guest displacement from host-guest complexes.

The preparation of single crystals of sparingly soluble polycyclic aromatic compounds in MeCN is facilitated by solubilizing ionic host-guest complexation under otherwise poor solvent conditions. The guest is then crystallized within minutes through controlled guest displacement from the host via competitor equilibria, or over days through direct crystallization of the host-guest complex itself.

In vitro production of N-degron fused proteins and its application.

The N-degron pathway, first discovered several decades ago by Varshavsky's laboratory, controls the half-life of target proteins depending on their N-terminal residues. In vivo cell biology studies have established the physiological role of the N-degron pathway. However, in vitro studies such as biochemical assays and structural biology studies are relatively limited. The N-degron substrates cannot be obtained via simple protein expression. The N-degron residues are exposed via the proteolytic process from the translated nascent polypeptide chains. Thus, methods for the fusion expression with several cleavable tags and subsequent treatment with specific proteases to design the exposed N-degron signals have been introduced. Recently, we developed a unique fusion technique using microtubule-associated protein 1A/1B light chain 3B (LC3B), a key marker protein of autophagy, to obtain a high yield of the purified target proteins with variable N-terminal residues for various biochemical studies including enzymatic and binding assays, and crystallization of N-degron complex. This chapter describes the protocols that include the vector map designed for producing LC3B fused target proteins, methods for expression and purification of an example protein, p62/SQSMT1, using different N-terminal residues, and methods to obtain the purified ATG4B protease, which is used for processing LC3B tag and exposing the required N-terminal residues of the target protein.

Light-driven flagella-like motion of coordination compound single crystals.

Single crystals of coordination complexes that show mechanical motion under the influence of external stimuli are of great interest due to their applications in photoactuators, sensors and probes. The solid-state [2+2] cycloaddition reaction has been one of the most prominent chemical reactions for photoresponsive materials in recent years. However, a relatively limited number of compounds have been reported, and most of these compounds have only shown destructive photosalient effects. Here, we report two photoreactive Zn(II) metal complexes with a thiophene-based photoreactive linker, 2tpy (4-(2-(thiophen-2-yl)vinyl)pyridine). In addition, under photoirradiation these complexes showed flagella-like bending, first towards and subsequently away from the excitation light source. This is the first report of metal-complexes and the solid-state [2+2] cycloaddition reaction that presents flagella-like motion in single crystals.

Discovery and development of inhibitors of acetyltransferase Eis to combat Mycobacterium tuberculosis.

Aminoglycosides are bactericidal antibiotics with a broad spectrum of activity, used to treat infections caused mostly by Gram-negative pathogens and as a second-line therapy against tuberculosis. A common resistance mechanism to aminoglycosides is bacterial aminoglycoside acetyltransferase enzymes (AACs), which render aminoglycosides inactive by acetylating their amino groups. In Mycobacterium tuberculosis, an AAC called Eis (enhanced intracellular survival) acetylates kanamycin and amikacin. When upregulated as a result of mutations, Eis causes clinically important aminoglycoside resistance; therefore, Eis inhibitors are attractive as potential aminoglycoside adjuvants for treatment of aminoglycoside-resistant tuberculosis. For over a decade, we have studied Eis and discovered several series of Eis inhibitors. Here, we provide a detailed protocol for a colorimetric assay used for high-throughput discovery of Eis inhibitors, their characterization, and testing their selectivity. We describe protocols for in vitro cell culture assays for testing aminoglycoside adjuvant properties of the inhibitors. A procedure for obtaining crystals of Eis-inhibitor complexes and determining their structures is also presented. Finally, we discuss applicability of these methods to discovery and testing of inhibitors of other AACs.

A coarse-grained molecular model of amyloid fibrils systems.

We report a computational model for amyloid fibrils and discuss its main features and ability to match different experimental morphological characteristics. The model captures the liquid crystalline and cholesteric behaviours in short and rigid amyloid fibrils and shows promising extendibility to more complex colloidal liquid crystals.

Dynamics in the ordered and disordered phases of barocaloric adamantane.

High-entropy order-disorder phase transitions can be used for efficient and eco-friendly barocaloric solid-state cooling. Here the barocaloric effect is reported in an archetypal plastic crystal, adamantane. Adamantane has a colossal isothermally reversible entropy change of 106 J K-1 kg-1. Extremely low hysteresis means that this can be accessed at pressure differences less than 200 bar. Configurational entropy can only account for about 40% of the total entropy change; the remainder is due to vibrational effects. Using neutron spectroscopy and supercell lattice dynamics calculations, it is found that this vibrational entropy change is mainly caused by softening in the high-entropy phase of acoustic modes that correspond to molecular rotations. We attribute this difference in the dynamics to the contrast between an 'interlocked' state in the low-entropy phase and sphere-like behaviour in the high-entropy phase. Although adamantane is a simple van der Waals solid with near-spherical molecules, this approach can be leveraged for the design of more complex barocaloric molecular crystals. Moreover, this study shows that supercell lattice dynamics calculations can accurately map the effect of orientational disorder on the phonon spectrum, paving the way for studying the vibrational entropy, thermal conductivity, and other thermodynamic effects in more complex materials.

Major Causes of Age Distortion in Uranium-Lead Isotopic Radiogeochronology

The causes of isotopic age distortion that may occur during the dating of endogenous geological processes (rocks) by the uranium-lead isotopic method are considered. Three groups of reasons are distinguished: mineralogical, geochemical and analytical. The main mineralogical reason for the distortion of the U-Pb isotopic age is the multistage crystallization of geochronometer minerals, which is manifested, for example, in zircon, in the anatomy of their crystals. It was concluded that in order to obtain reliable information about the time course of geological processes for complex crystals (primarily zircon), local uranium-lead isotope dating methods ("SHRIMP", LA-ICP-MS, etc.) should be used. The geochemical reasons include the discrepancy between the isotopic composition of impurity lead and the isotopic composition of corrective lead (abnormal isotopic composition of ordinary lead) and the polystage history of the development of the uranium-lead isotope system. It is noted that the most probable reason for the violation of the uranium-lead isotope system by zircons in the hypergenesis zone is the entrapment of uranium by defects in the crystal structure and cracks, and the predominant loss of uranium in monazite. At the same time, the loss of uranium by monazites depends on the composition of the acids. It is indicated that washing monazites in a weak solution of nitric acid leads to the appearance of a significant reverse discordance, while no loss of lead is observed. The same operation in a weak solution of hydrochloric acid leads to the preferential leaching of ordinary lead. For analytical reasons, the lowest accuracy of determining the prevalence of the 204Pb isotope (204Pb/206Pb ratio) is indicated. The impact of contamination of samples dated (method TIMS) by lead and uranium from reagents is considered. It is clear that the contamination of multi-grain samples (1-2 mlg) of minerals with uranium and lead from reagents with a modern isotopic composition, in a blank test of lead 10–9 g (the ratio of the mass of Pb of the sample to the mass of Pb from the reagents of 40 to 1) is not significant affects dating results (isotopic ratios of 207Pb/206Pb, 207Pb/235U and 206Pb/238U). A blank sample of uranium is usually 2 orders of magnitude smaller (10–11-10–12 g). A strong inverse relationship between the degree (proportion) of radiogenic lead contamination of radiogenic lead aliquots on the isotopic composition of lead and the calculated values of the lead content in the sample was revealed. When an aliquot for determining the content of uranium and lead is contaminated with ordinary lead from the reagents, the smallest distortion of the calculated value of the lead content occurs when the ratio of sample lead to tracer lead is 1:1, while a slightly smaller relative distortion of the lead content is noted with increasing age of the radiogenic lead of the samples.

Understanding and controlling the nucleation and growth of metal-organic frameworks.

Metal-organic frameworks offer a diverse landscape of building blocks to design high performance materials for implications in almost every major industry. With this diversity stems complex crystallization mechanisms with various pathways and intermediates. Crystallization studies have been key to the advancement of countless biological and synthetic systems, with MOFs being no exception. This review provides an overview of the current theories and fundamental chemistry used to decipher MOF crystallization. We then discuss how intrinsic and extrinsic synthetic parameters can be used as tools to modulate the crystallization pathway to produce MOF crystals with finely tuned physical and chemical properties. Experimental and computational methods are provided to guide the probing of MOF crystal formation on the molecular and bulk scale. Lastly, we summarize the recent major advances in the field and our outlook on the exciting future of MOF crystallization.

Zinc(II) and copper(II) complexes with N-substituted imines derived from 4-amino-1,2,4-triazole: Synthesis, crystal structure, and biological activity

Reactions of copper(II) and zinc(II) acetates with polynitrogen Schiff bases, namely 4-(pyridin-2-yl)methyleneamino-1,2,4-triazole (L1), 4-(pyridin-3-yl)methyleneamino-1,2,4-triazole (L2) and 4-(pyridin-4-yl)methyleneamino-1,2,4-triazole (L3), were studied. The reaction of Zn(OAc)2·2H2O and L1 gave crystals of trinuclear complex [Zn3(OAc)6(L1)2] (1). A similar reaction of Zn(OAc)2·2H2O and L2 resulted in 1D coordination polymer [Zn(OAc)2(L2)]n (2). The reactions of Cu(OAc)2·H2O with L2 or L3 gave crystals of 1D coordination polymer {[Cu2(OAc)4(L2)]·2MeCN}n (3) and binuclear complex [Cu2(OAc)2(L3)2]·2MeCN (4), respectively. The structures of the coordination compounds thus obtained were determined by single-crystal X-ray diffraction analysis. Complexes 1–4 demonstrated better antibacterial and antifungal activities in comparison with free L1, L2, and L3 ligands: the strongest antimicrobial activity was observed against E. coli for 2 and 3, and the highest antifungal activity was found for 1 and 2.