Yellow Single Crystals Research Articles

Structural design and characterization of a new type of organic nonlinear optical flavanone crystal

Two new crystals were designed and obtained: the chalcone derivative HMMP (1-(2‑hydroxy-4-methoxyphenyl)-3-(4-(methylthio)phenyl)prop‑2-en-1-one) and the flavanone derivative 7M4MC (7‑methoxy-2-(4-(methylthio)phenyl)chroman-4-one). Yellow bulk 7M4MC single crystal with dimensions of 3 × 2 × 1 mm3 and orange-yellow needle-like HMMP single crystal were grown by solution evaporation. 7M4MC crystal belongs to the P21 space group of the monoclinic structure, which has a non-centrosymmetric structure. HMMP crystal monoclinic, belongs to the P21/m space group with a centrosymmetric structure. In the 7M4MC molecule, the methoxy and methylthio groups act as electron donors (D) and the carbonyl group acts as an electron acceptor (A), forming a d-π-A-π-D structure with an electron gradient. 7M4MC exhibits a high degree of second-harmonic generation intensity (11 × KDP), a broad transmission range (600–1600 nm, >88 %), an elevated optical energy bandgap (Eg = 2.57 eV), high thermal stability (Tm = 105 °C) and excellent dielectric properties (εr ≈ 2.1). This work not only provides two new crystals but also offers a viable molecular design option by changing the degree of intramolecular distortion by altering the backbone structure.

Synthesis and crystal structure of Pb14.66Sn7.34Br26(CN2)7O2, a complex member of group 14 carbodiimides

AbstractA mixed lead/tin bromide carbodiimide oxide was synthesized by solid‐state reaction between Pb(CN2), PbBr2, SnBr2 and SnO at 400 °C. Its monoclinic crystal structure was solved and refined in the space group C2/m by single‐crystal X‐ray diffraction from a yellow single crystal. One crystallographic site was found to be occupied by both tin and lead, in agreement with the results of energy‐dispersive X‐ray spectroscopy (EDX). The crystal structure comprises a complex network of tin/lead tetrahedra and tin/lead trigonal bipyramids linked by NCN units. In contrast to Pb(CN2), where the NCN ion is present as a cyanamide moiety, IR‐spectroscopy of the title compound revealed the carbodiimide character of the NCN ion.

Cis and trans isomers of 1-(5-bromothiophen-2-yl)-3-(10-chloroanthracen-9-yl)prop-2-en-1-one: Synthesis and characterization

Chalcone derivatives are simple chemical scaffold found in natural products and have been extensively used as an effective template in medicinal chemistry for drug discovery. Two new geometrical isomers of 1-(5-bromothiophen-2-yl)-3-(10-chloroanthracen-9-yl)prop-2-en-1-one were synthesized, isolated and characterized by various spectroscopic techniques (FT-IR, NMR, LC-MS and UV-visible). Two different shaped (cis and trans) yellow colored single crystals were obtained by slow evaporation method and the molecular structures were confirmed by X-ray diffraction studies. The cis configuration crystallizes in the monoclinic P21/c space group, whereas, trans configuration crystallizes in the orthorhombic P212121 space group. The conformational changes lead to variations in molecular packing arrangement. In cis, 2-D layer-like architecture is constructed by C-H…O and S…S contacts, whereas, in trans 3-D zig-zag pattern is generated by C-H…O, C-H…Cl and Br…π interactions. The unique supramolecular topology of the isomers established by diverse intra and intermolecular interactions was analysed by Hirshfeld surfaces, 2D fingerprint plots, 3D energy framework and NCI index model. The Frontier molecular orbitals explored HOMO-LUMO energy gap and associated electronic properties were calculated. The molecular electrostatic potential (MEP) was plotted to identify the reactive sites in the molecule.

The Triclinic Lanthanoid(III) Halide Oxidoarsenates(III) Sm3Cl2[As2O5][AsO3] and Tm3Br2[As2O5][AsO3

Pale yellow single crystals of the composition Ln3X2[As2O5][AsO3] (Ln = Tm for X = Br and Ln = Sm for X = Cl) were obtained via solid‐state reactions in the systems Ln2O3/As2O3 from sealed silica ampoules using different halides as fluxing agents. Sm3Cl2[As2O5][AsO3] and Tm3Br2[As2O5][AsO3] crystallize isotypically in the triclinic space group P1 with Z = 2 and cell parameters of a = 543.51(4) pm, b = 837.24(6) pm, c = 1113.45(8) pm, α = 90.084(2)°, β = 94.532(2)°, γ = 90.487(2)° for the samarium and a = 534.96(4) pm, b = 869.26(6) pm, c = 1081.84(8) pm, α = 90.723(2)°, β = 94.792(2)° γ = 90.119(2)° for the thulium compound. The isotypic crystal structure of both representatives exhibits three crystallographically different Ln3+ cations, each with a coordination number of eight. (Ln1)3+ and (Ln2)3+ are only coordinated by three oxygen atoms, whereas (Ln3)3+ shows additional contacts to halide anions in forming square [LnO4X4]9– antiprisms. All As3+ cations are surrounded by three oxygen atoms in the shape of isolated [AsO3]3– ψ1‐tetrahedra. They occur either isolated or condensed as pyroanionic [As2O5]4– units with a bridging oxygen atom. In both anions, non‐binding lone‐pair electrons are present at the As3+ cations with a pronounced stereochemically active function.

Luminescent Properties of DOBDC Containing MOFs: The Role of Free Hydroxyls.

A novel metal-organic framework (MOF), Mn-DOBDC, has been synthesized in an effort to investigate the role of both the metal center and presence of free linker hydroxyls on the luminescent properties of DOBDC (2,5-dihydroxyterephthalic acid) containing MOFs. Co-MOF-74, RE-DOBDC (RE-Eu and Tb), and Mn-DOBDC have been synthesized and analyzed by powder X-ray diffraction (PXRD) and the fluorescent properties probed by UV-Vis spectroscopy and density functional theory (DFT). Mn-DOBDC has been synthesized by a new method involving a concurrent facile reflux synthesis and slow crystallization, resulting in yellow single crystals in monoclinic space group C2/c. Mn-DOBDC was further analyzed by single-crystal X-ray diffraction (SCXRD), scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS), and photoluminescent emission. Results indicate that the luminescent properties of the DOBDC linker are transferred to the three-dimensional structures of both the RE-DOBDC and Mn-DOBDC, which contain free hydroxyls on the linker. In Co-MOF-74 however, luminescence is quenched in the solid state due to binding of the phenolic hydroxyls within the MOF structure. Mn-DOBDC exhibits a ligand-based tunable emission that can be controlled in solution by the use of different solvents.

Synthesis, structure and physico-chemical properties of two uranyl complexes of cucurbiturils mediated by sulfate ions

In this article, with the aid of additional ligands, (UO2)2(CB5)(SO4)2(H2O)2•5H2O ( U-CB5-SO 4 ) and (UO2)-(CB6)0.5(SO4)(H2O)•4H2O ( U-CB6-SO 4 ) were synthesized by hydrothermal method at high temperature. Their structures and physico-chemical properties were characterized by a combination of single-crystal X-ray diffraction, PXRD, TG-DSC, FTIR, UV-Vis and fluorescence spectra. U-CB5-SO 4 crystalized in orthorhombic system, and space group Pnma , while U-CB6-SO 4 crystalized in monoclinic system and space group I2/m . U-CB5-SO 4 forms a yellow windmill-like poly crystal, while U-CB6-SO 4 forms a yellow stick-like single crystal.

Small Structural Changes in the Alkyl Substituents of Macrocyclic π-Extended Thiophene Oligomers Causes a Key Effect on Their Stacking and Functional Properties.

Three new macrocyclic π-extended thiophene hexamers composed of four thienylene-ethynylene and two thienylene-vinylene units with or without four alkyl substituents have been synthesized. Despite similar shape-persistent structures in solution, the alkyl substituents control the solid-state structures and morphologies. The unsubstituted hexamer exhibited a planar conformation with a theoretically predicted structure in the solid state; however, the planar hexamer with four ethyl substituents formed a closely stacked columnar crystal structure to exhibit π-π interactions. Interestingly, the hexamer with four butyl substituents adopted both planar and twisted conformations in the solid state, exhibiting polymorphism based on induced-fit stacking of molecules. Thus, the butyl-substituted hexamer produces a mixture of yellow, orange, and red single crystals from toluene/acetone, and X-ray analysis revealed six different conformations. Consequently, the small structural difference in the macrocycles causes a key effect on their functional properties in the solid state, and their morphology governs electrical conductivity and organic field-effect-transistor activity. The polymorphism of the hexamers was applied to the switching of film morphology.

Synthesis and investigation into the structural, electronic and electrical properties of K2Pb(OCN)I3.

Yellow transparent single crystals of the new compound K2Pb(OCN)I3 were synthesized from a mixture of lead iodide and potassium cyanate through a solid-state reaction, which was controlled by the differential scanning calorimetry (DSC) technique. The single crystal X-ray refinement showed that K2Pb(OCN)I3 crystallizes in the cubic system (Fd3[combining macron]m, a = 16.295(2) Å, V = 4327(1) Å3, Z = 16 and R1 = 0.0167). The structure is basically composed of two frameworks built from potassium tetrahedra capped by OCN- units and corner-sharing lead iodide octahedra. The infrared spectrum of K2Pb(OCN)I3 reveals the presence of vibration modes that were assigned to cyanate ions. The band structure and total and partial density of states calculated by DFT with the PBE functional (CASTEP code) showed that this compound exhibits a direct band gap of 2.19 eV, which is in good agreement with the experimental value obtained from a diffuse reflectance measurement (2.4 eV). The investigation of the electrical properties of this material demonstrates that it is highly resistive and has large permittivity (relative values of up to 104 at 150 °C). However, it does not display ferroelectric behavior.

Synthesis, characterization and the role of ionic radii on the mechanistic of solvothermal for polyazine PtIV complexes: Reduction PtIV to PtII, DFT, X-ray single crystal and anticancer studies

Polypyridyl based on triazine and pyrazine rings with Pt4+, including 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPT, L1) and 2,3,5,6-tetra(2-pyridyl)-1,4-triazine (TPP, L2), was reported. [Pt34+ (TPT)2Cl8]Cl4·2H2O (1) and [Pt4+(TPP)Cl3]Cl·3H2O (2) were synthesized and characterized. Comparative studies of the solvothermal of Pt4+ complexes and the stability studies of triazine and pyrazine moieties were investigated. Pt2+ complex, [PtII(bpca)Cl], resulted from the metal-promoted solvolysis of L1 to bis-(2-pyridylcarbonyl) amide anion (bpca) and 2-picolinamide, gives yellow single crystal, C12H8ClN3O2Pt (3). The effect of ionic radii of the metal ions has a vital role in solvolysis process. The single crystal shows a square-planar around the Pt2+ ion (3). Crystal data of 3: space group; a = 7.5263 (2) b = 14.1846 (4) c = 22.6884 (7) Å, α = β = γ = 90°, V = 2422.16 (12) Å3, Z = 8. The DFT parameters were calculated to confirm the geometry of complexes. Anticancer activity of complexes was measured.

Synthesis, characterization and the role of ionic radii on the mechanistic of solvothermal for polyazine PtIV complexes: Reduction PtIV to PtII, DFT, x-ray single crystal and anticancer studies

Polypyridyl based on triazine and pyrazine rings with Pt4+, including 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPT, L1) and 2,3,5,6-tetra(2-pyridyl)-1,4-triazine (TPP, L2), was reported. [Pt34+ (TPT)2Cl8]Cl4·2H2O (1) and [Pt4+(TPP)Cl3]Cl·3H2O (2) were synthesized and characterized. Comparative studies of the solvothermal of Pt4+ complexes and the stability studies of triazine and pyrazine moieties were investigated. Pt2+ complex, [PtII(bpca)Cl], resulted from the metal-promoted solvolysis of L1 to bis-(2-pyridylcarbonyl) amide anion (bpca) and 2-picolinamide, gives yellow single crystal, C12H8ClN3O2Pt (3). The effect of ionic radii of the metal ions has a vital role in solvolysis process. The single crystal shows a square-planar around the Pt2+ ion (3). Crystal data of 3: space group; a = 7.5263 (2) b = 14.1846 (4) c = 22.6884 (7) Å, α = β = γ = 90°, V = 2422.16 (12) Å3, Z = 8. The DFT parameters were calculated to confirm the geometry of complexes. Anticancer activity of complexes was measured.

Single Crystal Growth of Sillén–Aurivillius Perovskite Oxyhalides Bi4NbO8X (X = Cl, Br)

Sillén–Aurivillius perovskite Bi4NbO8X (X = Cl, Br) is a promising photocatalyst for water splitting under visible light, as well as a potential ferroelectric material. In this work, we investigate the crystal growth conditions by mainly varying soak temperature, soak time and cooling rate. Under the optimal conditions, we successfully obtained yellow platelet single crystals with an in-plane distance of several hundred microns. As opposed to conventional crystal growth, a moderate cooling is essential to suppress an evaporation of the Bi–O–Cl species from a melt zone. The single crystals of Bi4NbO8Br were also grown using a similar condition. We suggest that the knowledge obtained in this study can be generally applied to other Sillén–Aurivillius phases and related oxyhalides.

Dual-sensitive charge-conversional polymeric prodrug for efficient co-delivery of demethylcantharidin and doxorubicin

Polypyridyl based on triazine and pyrazine rings with Pt4+, including 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPT, L1) and 2,3,5,6-tetra(2-pyridyl)-1,4-triazine (TPP, L2), was reported. [Pt34+ (TPT)2Cl8]Cl4·2H2O (1) and [Pt4+(TPP)Cl3]Cl·3H2O (2) were synthesized and characterized. Comparative studies of the solvothermal of Pt4+ complexes and the stability studies of triazine and pyrazine moieties were investigated. Pt2+ complex, [PtII(bpca)Cl], resulted from the metal-promoted solvolysis of L1 to bis-(2-pyridylcarbonyl) amide anion (bpca) and 2-picolinamide, gives yellow single crystal, C12H8ClN3O2Pt (3). The effect of ionic radii of the metal ions has a vital role in solvolysis process. The single crystal shows a square-planar around the Pt2+ ion (3). Crystal data of 3: space group; a = 7.5263 (2) b = 14.1846 (4) c = 22.6884 (7) Å, α = β = γ = 90°, V = 2422.16 (12) Å3, Z = 8. The DFT parameters were calculated to confirm the geometry of complexes. Anticancer activity of complexes was measured.

An intelligent doxorubicin prodrug with GRP78 recognition and sequential targeting ability to tumor cell membrane and nucleus

Polypyridyl based on triazine and pyrazine rings with Pt4+, including 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPT, L1) and 2,3,5,6-tetra(2-pyridyl)-1,4-triazine (TPP, L2), was reported. [Pt34+ (TPT)2Cl8]Cl4·2H2O (1) and [Pt4+(TPP)Cl3]Cl·3H2O (2) were synthesized and characterized. Comparative studies of the solvothermal of Pt4+ complexes and the stability studies of triazine and pyrazine moieties were investigated. Pt2+ complex, [PtII(bpca)Cl], resulted from the metal-promoted solvolysis of L1 to bis-(2-pyridylcarbonyl) amide anion (bpca) and 2-picolinamide, gives yellow single crystal, C12H8ClN3O2Pt (3). The effect of ionic radii of the metal ions has a vital role in solvolysis process. The single crystal shows a square-planar around the Pt2+ ion (3). Crystal data of 3: space group; a = 7.5263 (2) b = 14.1846 (4) c = 22.6884 (7) Å, α = β = γ = 90°, V = 2422.16 (12) Å3, Z = 8. The DFT parameters were calculated to confirm the geometry of complexes. Anticancer activity of complexes was measured.

Synthesis and X‐ray Crystallography of Two Lead(II) Decahydro‐closo‐Decaborate Hydrates

The reaction of Pb[CO3] with an aqueous solution of (H3O)2[B10H10] in an equimolar ratio leads to two lead(II) decahydro‐closo‐decaborate hydrates both as triclinic, pale yellow single crystals. The water‐rich compound with the formula [Pb(H2O)3]2Pb[B10H10]3·5.5H2O crystallizes in the space group P1 (a = 711.72(4), b = 1243.14(8), c = 2064.83(12) pm, α = 81.806(3), β = 83.795(3), γ = 80.909(3)°) with Z = 2. The compound with the lower water content, [Pb(H2O)3]Pb[B10H10]2·1.5H2O, also crystallizes in P1 (a = 718.46(4), b = 1288.75(8), c = 1279.91(8) pm, α = 70.145(3), β = 75.976(3), γ = 80.324(3)°) with Z = 2. Both structures can be described as layered arrangements and contain one Pb2+ cation each, which is only coordinated by the hydridic hydrogen atoms of the hydroborate anions. All the others are primarily surrounded by three water molecules in a non‐planar fashion and additional hydrogen atoms of [B10H10]2– anions. The non‐lead‐bonded crystal water molecules in both structures are all connected via hydrogen bonds to the water molecules, which coordinate the Pb2+ cations, as well as via non‐classical hydrogen bonds to the cluster anions and reside between the layers. The [B10H10]2– anions show only slight distortions from their ideal shape as bicapped square antiprisms.

The new one-dimensional coordination polymer catena-poly[[diaquasodium(I)]-μ-oxalato-[diaquairon(III)]-μ-oxalato

The oxalate dianion is one of the most studied ligands and is capable of bridging two or more metal centres and creating inorganic polymers based on the assembly of metal polyhedra with a wide variety of one-, two- or three-dimensional extended structures. Yellow single crystals of a new mixed-metal oxalate, namely catena-poly[[diaquasodium(I)]-μ-oxalato-κ(4)O(1),O(2):O(1'),O(2')-[diaquairon(III)]-μ-oxalato-κ(4)O(1),O(2):O(1'),O(2')], [NaFe(C2O4)2(H2O)4]n, have been synthesized and the crystal structure elucidated by X-ray diffraction analysis. The compound crystallizes in the noncentrosymmetric space group I41 (Z = 4). The asymmetric unit contains one Na(I) and one Fe(III) atom lying on a fourfold symmetry axis, one μ2-bridging oxalate ligand and two aqua ligands. Each metal atom is surrounded by two chelating oxalate ligands and two equivalent water molecules. The structure consists of infinite one-dimensional chains of alternating FeO4(H2OW1)2 and NaO4(H2OW2)2 octahedra, bridged by oxalate ligands, parallel to the [100] and [010] directions, respectively. Because of the cis configuration and the μ2-coordination mode of the oxalate ligands, the chains run in a zigzag manner. This arrangement facilitates the formation of hydrogen bonds between neighbouring chains involving the H2O and oxalate ligands, leading to a two-dimensional framework. The structure of this new one-dimensional coordination polymer is shown to be unique among the A(I)M(III)(C2O4)2(H2O)n series. In addition, the absorption bands in the IR and UV-Visible regions and their assignments are in good agreement with the local symmetry of the oxalate ligand and the irregular environment of iron(III). The final product of the thermal decomposition of this precursor is the well-known ternary oxide NaFeO2.

Structural characterization and nonlinear optical properties of 1-phenyl-3-(4-bis(2-chloroethyl)aminophenyl)-2-propen-1-one

A new chalcone derivative 1-phenyl-3-(4-bis(2-chloroethyl)aminophenyl)-2-propen-1-one with the molecular formula C19H19Cl2NO is synthesized by the Claisen–Schmidt condensation reaction. A transparent yellow single crystal was obtained by the slow evaporation solution growth technique using ethanol at room temperature. The compound crystallizes in the triclinic crystal system, P-1 space group, Z = 4, calculated density = 1.332 mg/m3, V = 1736.00(8) A3 with unit cell parameters a = 7.8899(2) A, b = 14.1924(4) A, c = 15.7879(4) A, α = 83.1280(10)°, β = 81.929(2)°, γ =86.4820°. The second harmonic generation efficiency is found to be 1.5 times higher than that of urea. Thermal stability of the crystal is found to be 250°C determined from the thermogravimetric analysis. The FT-IR spectroscopy is used to identify the functional groups of the synthesized compound. The optical behavior of the grown crystal is examined by the UV-visible spectral analysis, which shows that the absorbance is almost negligible in the wavelength range 400-1300 nm.

ChemInform Abstract: Crystal Growth and Structure of the Barium Chloride Nitridotantalate(V) Ba3Cl2TaN3.

AbstractTransparent, light yellow single crystals of the new title compound are obtained from the reaction of Ba(N3)Cl with the container wall of arc‐welded Ta ampules (900 °C, 4 d).

Crystal Growth and Structure of the Barium Chloride Nitrido­tantalate(V) Ba3Cl2TaN3

AbstractTransparent, light yellow single crystals of the barium chloride nitridotantalate(V) Ba3Cl2TaN3 (hexagonal, P63cm; a = 1507.39(8) pm, c = 632.98(3) pm, c/a = 0.420; Z = 6) are obtained by the reaction of the barium azide chloride Ba(N3)Cl or its ternary decomposition products with the container wall of arc‐welded tantalum ampoules at 900 °C after four days. Its crystal structure displays one‐dimensional chains 1∞{[TaN2/2N2/1]4–} consisting of corner‐sharing [TaN4]7– tetrahedra (d(Ta–N) = 191–200 pm), which run along [001] and arrange as hexagonal rod packing. Charge compensation of these parallel 1∞{[TaN3]4–} strands occurs via Ba2+ cations and Cl– anions erecting a three‐dimensional network 3∞{[Ba3Cl2]4+} (d(Ba–Cl) = 318–339 pm) with narrow channels apt to embed the chains. Several Ba–N contacts ranging between 264 and 319 pm secure the interconnection between both structural arrays and complete the coordination numbers of the Ba2+ cations to seven or eight.

Cracking the Dumbbell – from (NO)4[Pt2(SO4)5] to (NO)2[Pt(S2O7)3] by Oxidation with SO3

AbstractThe reaction of elemental platinum, oleum (65 % SO3), and fuming nitric acid in sealed glass ampoules at 350 °C yielded orange single crystals of (NO)4[Pt2(SO4)5] [triclinic, P$\bar{1}$, Z = 4, a = 977.41(3) pm, b = 1318.37(4) pm, c = 1511.47(5) pm, α = 105.218(1)°, β = 95.042(1)°, γ = 102.293(1)°, V = 1814.80(1)·106 pm3]. The crystal structure contains dumbbell shaped [Pt2] moieties surrounded by four chelating sulfate anions, forming the so‐called paddlewheel motif. The paddlewheels are connected via two terminal monodentate sulfate anions to infinite anionic chains. Charge compensation is achieved by nitrosylium cations. The reaction of (NO)4[Pt2(SO4)5] with neat SO3 in sealed glass ampoules at 120 °C yielded yellow single crystals of the tris‐(disulfato)‐platinate(IV) (NO)2[Pt(S2O7)3] [triclinic, P$\bar{1}$, Z = 2, a = 893.20(4) pm, b = 1093.25(4) pm, c = 1098.63(4) pm, α = 62.329(2)°, β = 69.107(2)°, γ = 69.654(2)°, V = 865.88(6)·106 pm3]. In the structure of (NO)2[Pt(S2O7)3] the platinum atoms are coordinated by three bidentate chelating disulfate anions forming an octahedral coordination sphere of oxygen atoms around the platinum atom. Charge compensation is achieved by nitrosylium cations. The thermal behavior of both compounds was monitored by TG/DSC measurements. Magnetic susceptibility measurements on (NO)2[Pt(S2O7)3] revealed diamagnetism, proving the electronic d6 low‐spin configuration of the Pt4+ ion.

ChemInform Abstract: Oxidizing Elemental Platinum with Oleum under Harsh Conditions: The Unique Tris(disulfato)platinate(IV) [Pt(S2O7)3]2‐ Anion.

AbstractDirect oxidation of elemental Pt by oleum (65% SO3) in the presence of BaCO3 yields yellow single crystals of Ba[Pt(S2O7)3] (H2SO4)0.5 (H2S2O7)0.5 (sealed glass ampoule, 160 °C).