Showing papers in "Crystal Growth & Design in 2019"
TL;DR: A tutorial review aimed at both the novice and the seasoned solid-state chemist provides a succinct overview of key findings that have, over the last half century, advanced our ability to make molecular crystals with targeted structures and desired properties.
Abstract: This Tutorial Review, aimed at both the novice and the seasoned solid-state chemist, provides a succinct overview of key findings that have, over the last half century, advanced our ability to make molecular crystals with targeted structures and desired properties. The article critically evaluates the efficiency and reliability of the well-established guidelines used by experimentalists in crystal engineering and highlights statistical and computational tools that are both advantageous to crystal design and accessible to experimental solid-state chemists.
193 citations
TL;DR: In this paper, the updated concepts on the nature of π-π interactions and their use in various fields ranging from crystal engineering to materials science to biochemistry are discussed and discussed.
Abstract: The updated concepts on the nature of π–π interactions and their use in various fields ranging from crystal engineering to materials science to biochemistry are discussed. This is the opening paper...
188 citations
TL;DR: In this article, a pillar-layer luminescent metal-organic framework (MOF) was constructed for detecting SiF62-anion via luminescence enhancement effect, which can be used as a platform of recyclable multi-responsive sensor for Fe3+, Al3+SiF62−, Cr2O72−, Nitrofurantoin (NFT), and nitrofurazone (NFZ) in water.
Abstract: The hard–soft-acid–base (HSAB) and dual-ligand strategies have been used to construct a pillar-layer luminescent metal–organic framework (MOF) {[Zn2(TRZ)2(DBTDC-O2)]·DMAc}n (1), in which H2DBTDC-O2 = S,S-dioxodibenzothiophen-3,7-dicarboxylic acid and HTRZ = 1,2,4-triazole. Thanks to its high stability in water and quadrangle microporous channels, MOF 1 can be served as a platform of recyclable multi-responsive luminescent sensor for Fe3+, Al3+, SiF62–, Cr2O72–, nitrofurantoin (NFT), and nitrofurazone (NFZ) in water. This is the first MOF-based sensor for detecting SiF62– anion via luminescent enhancement effect. Significantly, 1 also represents a unique example to probe NFZ or NFT by using transition metal MOFs in water, which exhibits the most sensitive sensing ability for NFZ (Ksv = 5.2 × 104 M–1) and NFT (Ksv = 1.8 × 105 M–1) via luminescent quenching.
129 citations
TL;DR: The modular nature of metal–organic frameworks (MOFs) leads to a very large number of possible structures, and high-throughput computational screening has led to a rapid increase in property data that is compatible with MOFs.
Abstract: The modular nature of metal–organic frameworks (MOFs) leads to a very large number of possible structures. High-throughput computational screening has led to a rapid increase in property data that ...
106 citations
TL;DR: In this article, the authors reported hybrid NiCo2O4@NiWS, a core-shell-structured electrode material with superior electrochemical and electrocatalytic performance.
Abstract: It is very important to design hybrid core–shell structured electrode materials to obtain superior electrochemical and electrocatalytic performance. In this work, we reported hybrid NiCo2O4@NiWS na...
100 citations
TL;DR: In this article, hydrogen bonding (HB) universally exists in CHON-containing energetic materials (EMs) and significantly influences their structures, properties, and performances, as time proceeds, some new types o...
Abstract: Hydrogen bonding (HB) universally exists in CHON-containing energetic materials (EMs) and significantly influences their structures, properties, and performances. As time proceeds, some new types o...
92 citations
TL;DR: Two series of lanthanide metal-organic frameworks (MOFs) formulated as {Ln2(TBrTA)3(H2O)8·2H 2O}n [Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9)] series 1, series 2, respectively, were synthesized via slow evaporation with tetrabromoterephthalic acid and structurally characterized by X-ray
Abstract: Two series of lanthanide metal–organic frameworks (MOFs) formulated as {Ln2(TBrTA)3(H2O)8·2H2O}n [Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9)] series 1, {[Ln3(TBrTA)6][Ln(H2O)8]·6H2O}n [Ln = Ho (10), Er (11), Tm (12), Yb (13), Lu (14)] series 2, respectively, were synthesized via slow evaporation with tetrabromoterephthalic acid (H2TBrTA) and structurally characterized by X-ray crystallography, infrared spectroscopy, and thermal analysis. Lanthanide contraction effects result in a change in the structure from a two-dimensional (2D) MOF with sql topology for La–Dy (series 1) to a three-dimensional (3D) MOF with pcu network topology for Ho–Lu (series 2). Supramolecular interactions also evolve from Br···Br, Br···O, π–π, and hydrogen bonding interactions in series 1 to Br···Br and hydrogen bonding interactions in series 2. The nature of Br···Br interactions transition from a combination of type I, type II, and quasi-type I/type II in series 1 to only type II in series 2. Furth...
89 citations
TL;DR: In this article, the development of IR-NLO materials remains urgent because the exi cientity of IR nonlinear optical (IRNLO) materials remains low and hence the need for new materials remains high.
Abstract: Infrared nonlinear optical (IR-NLO) materials are the key components in solid-state lasers for military and civilian applications. The development of IR-NLO materials remains urgent because the exi...
86 citations
TL;DR: In this article, a significant potential has been demonstrated by these novel solids in terms of modifying the physicochemical properties of physicochemical compounds, and the potential of these solids has been explored.
Abstract: Cocrystals are long known yet recently applied molecular entities. In the past decade, a significant potential has been demonstrated by these novel solids in terms of modifying the physicochemical ...
79 citations
TL;DR: A two-dimensional, tetragonal porous metal organic framework was synthesized under hydrothermal conditions by employing 1,3,5-tri(1H-benzo[d]imidazol-1y) as mentioned in this paper.
Abstract: A two-dimensional, tetragonal porous metal organic framework {[Zn2(TBIB)2(HTCPB)2]·9DMF·19H2O}n (1) has been synthesized under hydrothermal conditions by employing 1,3,5-tri(1H-benzo[d]imidazol-1-y...
76 citations
TL;DR: In this paper, the discovery of efficient electromagnetic wave absorbing materials for solving serious electromagnetic wave pollution is an urgent task, and a new three-dimensional me-shaped model is proposed.
Abstract: The discovery of efficient electromagnetic wave absorbing materials for solving serious electromagnetic wave pollution is an urgent task. By rational design and assembly, a new three-dimensional me...
TL;DR: A set of databases that bear information on geometrical and topological properties of metal coordination centers and ligands in crystal structures from the Cambridge Structural Database are described, which can be used to derive correlations of "chemical composition – structure – property" in an automated mode then forming a knowledge database.
Abstract: We describe a set of databases that bear information on geometrical and topological properties of 1 281 254 metal coordination centers and 204 828 ligands in 593 879 crystal structures of coordination compounds from the Cambridge Structural Database. These databases contain a number of structural descriptors, which are calculated according to rigorous algorithms and can be used to derive correlations of “chemical composition – structure – property” in an automated mode then forming a knowledge database. Many examples of such correlations and possible applications of the databases for investigation and design of coordination compounds are considered.
TL;DR: A 3-fold interpenetrating 3D metal-organic framework was proposed in this article with a novel metalorganic framework {Zn 2(tpt)2(tad)2·H2O} (tpt = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine, H2tda = 2.5-thiophene dicarboxylic acid).
Abstract: A novel metal–organic framework {Zn2(tpt)2(tad)2·H2O} (tpt = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine, H2tda = 2,5-thiophene dicarboxylic acid) with a 3-fold interpenetrating 3D framework was success...
TL;DR: In this article, a polyfluorinated-aromatic carboxylic acid has been designed and synthesized by the acylation reaction, tetrafluoro-bis(3,5-dicarboxyphenyl)terephthalamide (H4 bdtfa), which assembled with Zn2+ ions in the mixed solvents of DMF, py, and H2O under solvothermal conditions to produce a two-dimensional coordination polymer (CP), {[Zn2(bdtfa)(py)3(H2O
Abstract: A polyfluorinated-aromatic carboxylic acid has been designed and synthesized by the acylation reaction, tetrafluoro-bis(3,5-dicarboxyphenyl)terephthalamide (H4 bdtfa), which assembled with Zn2+ ions in the mixed solvents of DMF, py, and H2O under solvothermal conditions to produce a two-dimensional (2D) coordination polymer (CP), {[Zn2(bdtfa)(py)3(H2O)]·2DMF}n (1), (py = pyridine, DMF = N,N′-dimethylmethanamide). The final structure has been carefully characterized by various methods including single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), infrared (IR) spectroscopy, and thermogravimetric analysis. Two types of four-coordinated Zn2+ centers present a 2D “sql”-type layer through bdtfa4– ligands, and the adjacent layers are connected through hydrogen bonds and π···π stacking interactions to produce a three-dimensional supramolecular framework. Luminescent results reveal that CP 1 can be regarded as a highly sensitive sensor for detecting nitroaromatics based on the fluorescence quenching...
TL;DR: Trimorphic paracetamol, one of the most commonly used analgesic and antipyretic drugs, has been a model system for studying transformations among phases of molecular crystalline materials.
Abstract: Trimorphic paracetamol, one of the most commonly used analgesic and antipyretic drugs, has been a model system for studying transformations among phases of molecular crystalline materials. During c...
TL;DR: A new 1:1 cocrystal explosive composed of 2,4,6,8,10,12-hexanitrohexaazaiso-wurtzitane (CL-20) and 1,4dinitroimidazole (1,4-DNI) was synthesized through cocrystallization by slow solvent evaporati as discussed by the authors.
Abstract: A new 1:1 cocrystal explosive composed of 2,4,6,8,10,12-hexanitrohexaazaiso-wurtzitane (CL-20) and 1,4-dinitroimidazole (1,4-DNI) was synthesized through cocrystallization by slow solvent evaporati...
TL;DR: In this article, the detection of hazardous and explosive nitro-aromatic compounds using metal-organic frameworks (MOFs) has been a promising research field in the curre...
Abstract: Because of serious environmental pollutions, the detection of hazardous and explosive nitro-aromatic compounds using metal–organic frameworks (MOFs) has been a promising research field in the curre...
TL;DR: In this paper, the bifunctional 1,4-bis(imidazol-1-yl)terephthalic acid (H2BTA)-based coordination polymers (CPs) have been synthesized and the gas adsorption behaviors of complexes 1 and 2 for N2, CO2, and CH4 have been studied in detail at varying temperatures.
Abstract: On the basis of the bifunctional 1,4-bis(imidazol-1-yl)terephthalic acid (H2BTA), four three-dimensional (3D) Pb(II)/Zn(II) coordination polymers (CPs), {[Zn(BTA)]·1.5(DOA)}n (1), [Zn(BTA)]n (2), [Pb(BTA)]n (3), and [Pb(BTA)]n (4), have been synthesized (DOA = dioxane). Structural analyses reveal that two Zn(II)-based complexes are 3D (4,4)-c pts pseudo-supramolecular isomers for 1 and 2, and two Pb(II)-based complexes are supramolecular isomers with a 3D (4,5,6)-c net for 3 and a 3D 6-c pcu net for 4, respectively. Furthermore, the gas adsorption behaviors of complexes 1 and 2 for N2, CO2, and CH4 have been studied in detail at varying temperatures, and the results showed that the adsorption capacities to CO2 at 273 K and 1 bar are stronger than those of other gases. Meanwhile, the selectivity of 1 and 2 for CO2/CH4 was evaluated by the usage of the ideal adsorbed solution theory, whose selectivity exceeded those of reported MOFs under similar conditions. In addition, the fluorescent measurements showed ...
TL;DR: The quaternary chalcogenides SrCdGeS4 and S4 were prepared by high-temperature reactions in the form of single crystals (at 1223 and 1123 K, respectively) or micro-crystalline samples (at 1023 K).
Abstract: The quaternary chalcogenides SrCdGeS4 and SrCdGeSe4 were prepared by high-temperature reactions in the form of single crystals (at 1223 and 1123 K, respectively) or microcrystalline samples (at 1023 K). They adopt non-centrosymmetric structures (orthorhombic, space group Ama2, Z = 4; a = 10.3352(14) A, b = 10.2335(14) A, c = 6.4408(9) A for SrCdGeS4; a = 10.8245(8) A, b = 10.6912(8) A, c = 6.6792(5) A for SrCdGeSe4) consisting of anionic [CdGeCh4]2– layers separated by Sr2+ cations. Although the structure is closely related to the BaZnSiSe4-type, the substitution of Cd for Zn is accompanied by a significant displacement away from an ideal tetrahedral site toward a trigonal pyramidal geometry. Relationships to other similar structures are also elucidated. Large optical band gaps of 2.6 eV for SrCdGeS4 and 1.9 eV for SrCdGeSe4 were deduced from the absorption edges, consistent with the light yellow and red colors, respectively, of crystals of these compounds. Nonlinear optical measurements on powder samples...
TL;DR: In this article, the water vapor pressure-temperature (p-T) phase diagram of the following thermochemical salts was constructed by combining equilibrium and nonequilibrium hydration experiments: CuCl 2, K 2 CO 3, MgCl 2 ·4H 2 O, and LiCl.
Abstract: The solid-state hydration of salts has gained particular interest within the frame of thermochemical energy storage. In this work, the water vapor pressure-temperature (p-T) phase diagram of the following thermochemical salts was constructed by combining equilibrium and nonequilibrium hydration experiments: CuCl 2 , K 2 CO 3 , MgCl 2 ·4H 2 O, and LiCl. The hydration of CuCl 2 and K 2 CO 3 involves a metastable zone of ca. 10 K, and the induction times preceding hydration are well-described by classical homogeneous nucleation theory. It is further shown for K 2 CO 3 (metastable) and MgCl 2 ·4H 2 O (not metastable) through solubility calculations that the phase transition is not mediated by bulk dissolution. We conclude that the hydration proceeds as a solid-solid phase transition, mobilized by a wetting layer, where the mobility of the wetting layer increases with increasing vapor pressure. In view of heat storage application, the finding of metastability in thermochemical salts reveals the impact of nucleation and growth processes on the thermochemical performance and demonstrates that practical aspects like the output temperature of a thermochemical salt are defined by its metastable zone width (MZW) rather than its equilibrium phase diagram. Manipulation of the MZW by e.g. prenucleation or heterogeneous nucleation is a potential way to raise the output temperature and power on material level in thermochemical applications. © Copyright 2019 American Chemical Society.
TL;DR: In this paper, five heteronuclear nickel(II)/lead(II) complexes with two compartmental reduced Schiff base ligands were characterized and their structures were confirmed by single crystal X-ray diffractors.
Abstract: Five heteronuclear nickel(II)/lead(II) complexes with two compartmental reduced Schiff base ligands were prepared and characterized. Their structures were confirmed by single crystal X-ray diffract...
TL;DR: In this paper, a metal-involving bifurcated halogen bonding was detected, by single-crystal XRD, along with other halomethane-chloride interactions.
Abstract: The complexes trans-[PtCl2(NCNR2)2] (R2 = Me2 1, Et2 2, (CH2)4 3) were cocrystallized with CBr4 in CHCl3 (1 and 3) or in MeNO2 (2) forming adducts 1·CHCl3·CBr4, 2·2CBr4, and 3·2CBr4, respectively. In two out of three adducts, viz. 1·CHCl3·CBr4 and 2·2CBr4, unique Br3C–Br···η2(Cl–Pt) metal-involving bifurcated halogen bonding was detected, by single-crystal XRD, along with other halomethane–chloride interactions. Appropriate density functional theory calculations performed by two complementary methodologies, (i) single-point “quasi-solid state” calculations with topological analysis of the electron density distribution within the framework of Bader theory (QTAIM method) and (ii) Kohn–Sham calculations with periodic boundary conditions, confirmed the existence of the bifurcated interactions and their noncovalent nature. Estimated energies of these interactions vary from 1.1 to 4.7 kcal/mol.
TL;DR: A doubly interpenetrated metal-organic framework (MOF) was first synthesized by employing a rigid 2,6-bis(4′-carbo....
Abstract: A doubly interpenetrated metal–organic framework (MOF) [Zn4(L)3O]·8DMF·H2O (1, DMF = N,N-dimethylformamide) including the [Zn4O] clusters was first synthesized by employing a rigid 2,6-bis(4′-carbo...
TL;DR: In this paper, a simple substitution of organic linkers of IRMOF-1 (i.e., MOF-5) for other IRMOFs can be obtained.
Abstract: Isoreticular metal–organic frameworks (IRMOFs) are a series of MOFs that own similar network topology. By simple substitution of organic linkers of IRMOF-1 (i.e., MOF-5), other IRMOFs can be obtain...
TL;DR: In this article, the authors highlight the post-synthetic methods based on stepwise reactions including metal-ion metathesis, ligand exchange, and sequential linker installation, which has proven to be powerful for fabrication of desired MOFs that are not available by direct synthesis.
Abstract: Metal–organic frameworks (MOFs) have attracted much attention not only because of their diverse framework structures but also due to their interesting properties as well as potential applications in varied fields. The rational design and fabrication of MOFs with desired structures and properties are important but still a challenge. Generally, the construction of new MOFs is mainly by mixing metal salts/clusters and organic ligands via a conventional reaction process. However, the conventional reaction process is not always available for the targeted MOFs. In this review, we will highlight the postsynthetic methods based on stepwise reactions including metal-ion metathesis, ligand exchange, and sequential linker installation, which has been proven to be powerful for fabrication of desired MOFs that are not available by direct synthesis.
TL;DR: In this paper, a single crystal Na2Co2TeO6 has been successfully grown by self-flux method, and its lattice structure and basic magnetic properties were characterized.
Abstract: Single crystal Na2Co2TeO6 has been successfully grown by self-flux method, and its lattice structure and basic magnetic properties were characterized. As determined by single crystal X-ray diffraction, Na2Co2TeO6 belongs to space group P6322 (182) with a = b = 5.2709(2) A, c = 11.2615(15) A, and V = 270.95 (4) A3, the crystal structure is a layered honeycomb formed by CoO6 octahedra and the TeO6 octahedra in the center of the honeycomb layers, and the NaO6 octahedra are between the honeycomb layers. Magnetic susceptibility measurements indicate that the single crystal sample displays a distinct anisotropic behavior and the spin parallels the honeycomb plane (ab-plane). In a lower temperature region, a series of antiferromagnetic-like (AFM-like) phase transitions were observed, which may result from the spin reorientation of Co2+ ions. The different magnetization behavior between the polycrystalline structure and the single crystal (with the magnetic field parallel to and perpendicular to the ab-plane) rev...
TL;DR: In this paper, four two-dimensional, solvent-free metal primary explosives with powerful and reliable stabilities have been developed for use in the field of military and civilian technologies, respectively.
Abstract: Primary explosives with powerful and reliable stabilities have attractive applications in the field of military and civilian technologies. In this work, four two-dimensional, solvent-free metal azi...
TL;DR: The problem of pollution caused by highly toxic ions has become the focus of global attention and has attracted the interest of many researchers as discussed by the authors, however, microdetection using a metal-organic frame has attracted little attention.
Abstract: The problem of pollution caused by highly toxic ions has become the focus of global attention and has attracted the interest of many researchers. However, microdetection using a metal–organic frame...
TL;DR: A new phase of Ba3(C3N3O3)2 (I) was grown from RbCNO and BaCl2 by a solid state cyclo-trimerization reaction.
Abstract: A new phase of Ba3(C3N3O3)2 (I) was grown from RbCNO and BaCl2 by a solid state cyclo-trimerization reaction. It crystallizes in space group R3 with the cell parameters of a = 7.0934(2) A and c = 20.1130(9) A, featuring a layered structure stacked from the ∞2[Ba(C3N3O3)2]2– double layers along the c direction. I exhibits wide ultraviolet transparency and large optical anisotropy of Δn = 0.32 at 800 nm, two times than that of the benchmark birefringent crystal calcite. The discovery of I shows that replacement of calcite is conceivable and opens the novel pathway for designing novel ultraviolet birefringent crystals in metal cyanurates.
TL;DR: In this article, the authors defined cocrystal as a single-phase crystalline solid composed of two or multiple components in a stoichiometric ratio, and the components of a cocrystals can be atoms, molecules, anions and cations in pairs, and/or metallic cations with free electrons shared.
Abstract: “Cocrystal” is currently an increasingly popular term in the crystal community, as it has already been verified that the cocrystallization to form new crystals can serve as a promising strategy and an efficient technology to modulate and improve properties and performances of materials in the fields of pharmaceuticals and others. Nevertheless, the definition and intetsion of cocrystal still remain debatable. In this Perspective, we redefine cocrystal with a broadened intention as “a cocrystal is a single-phase crystalline solid composed of two or multiple components in a stoichiometric ratio, and the components of a cocrystal can be atoms, molecules, anions and cations in pairs, and/or metallic cations with free electrons shared”. Thereby, cocrystals are classified into five types in terms of the kinds of the components and their interactions in crystal entity, including atomic cocrystal, molecular cocrystal, ionic cocrystal, metallic cocrystal, and mixed-type cocrystal. The reasserted definition and broa...