Search Results (147)

The highly fluorescent fluorene group is of interest for its unique optical and electronic properties. By incorporating it into a metal complex, these properties are extended to the complex and are useful in a number of different applications. Four β-diketone ligands were synthesized containing the fluorene-functional group, where the varying substituent on the β-diketone was CF₃ (1), PhCF₃ (2), Ph (3) and PhCH₃ (4). The corresponding cyclooctadiene rhodium(I) complexes of the type [Rh(cod)((fluorene)COCHCOR)], with R = CF₃ (5), PhCF₃ (6), Ph (7) and PhCH₃ (8) were also synthesized. A crystal structure determination of 2 and 6 was performed, highlighting important changes in the ligand structure as a result of metal complexation. The structure of 2 also showed a hydrogen interaction between the hydroxy and carboxyl groups, forming a pseudo six-membered ring that stabilizes the enol form of the compound. Cyclic voltammetry (CV) of the β-diketones 1–4 showed a reduction wave for the reduction of the β-diketonato backbone between −1500 mV and −2100 mV as measured against ferrocene (FcH). CVs of rhodium(I) complexes 5–8 showed a reduction of the β-diketonato backbone between −1800 and −2000 mV, as well as an oxidation wave for the oxidation of the rhodium(I) metal centre at approximately 300 mV. Full article

Achieving high quantum yields for Yb³⁺ ion emission in complexes with organic ligands is a challenging task, as most Yb³⁺ complexes with such ligands typically exhibit efficiencies below 3.5%. Our research demonstrates that the introduction of heavy atom-containing ancillary ligands, such as TPPO or TPAO, along with the careful engineering of the main β-diketone ligand, can increase the luminescence efficiency up to 20-fold by the alteration of the energy migration pathway. It is demonstrated that the combination of two distinct organic ligands leads to the blockage of singlet–triplet intersystem crossing (ISC), alongside electronic energy transfer from β-diketone to Yb³⁺ ions through charge transfer states. The synthesized complexes exhibit quantum yields of 6.5% and 7.0% in the solid state, which places them at the top globally among this class of materials with simple non-deuterated and non-fluorinated ligands. Full article

The heteroleptic halogen-substituted Fe³⁺ complex of formula [FeL₂Bipy]Cl, where L is 1-(4-fluoro-phenyl)-3-(4-bromo-phenyl)-propane-1,3-dione and Bipy is 2,2′-bipyridine, was synthesized, and its optic and magnetic properties were studied. Magnetic measurements showed that the complex at high temperatures (T > 75 K) is predominantly in the high-spin (HS) state of Fe³⁺ ions (S = 5/2, γ_HS¹ = 93%) with a small admixture of low-spin (LS) state (S = 1/2, γ_LS¹ = 7%). At T* ≈ 46 K, a partial spin-crossover transition (SCO, 5/2↔1/2) occurs. This process is accompanied not only by a change in the magnetic state (γ_HS² = 76%, γ_LS² = 24%), but also by the appearance of AFM interactions (θ_II = −2.3 K) between neighboring Fe³⁺ ions. A theoretical model was proposed to describe magnetic susceptibility, χ(T). As a result of the analysis of the ground spin state M(H) at 2.0 K, it was established that the majority of the LS states, as well as part of the HS states of Fe³⁺ ions (γ_HS ~ 53%), do not participate in exchange interactions. EPR studies confirmed the presence of HS and LS Fe³⁺ centers and made it possible to isolate I-type and II-type HS centers, corresponding to strong low-symmetry and weak distorted octahedral fields. SCO was also detected and the temperature dependences of the EPR intensities, I(T), of the HS and LS centers were analyzed. Full article

Europium(III) β-diketone and organic carboxylic acid complexes are designable, easy to prepare, and easy to modify and have excellent fluorescence properties (narrow emission spectral band, high colour purity, long fluorescence lifetime, high quantum yield, and a spectral emission range covering both the visible and near-infrared regions). These complexes play important roles in popular fields such as laser and fibre-optic communications, medical diagnostics, immunoassays, fluorescent lasers, sensors, anticounterfeiting, and organic light-emitting diodes (OLEDs). In the field of light-emitting materials, europium complexes are especially widely used in OLED lamps, especially because of their high-efficiency emission of red (among the three primary colours); accordingly, these complexes can be mixed with blue and green phosphors to obtain high-efficiency white phosphors that can be excited by near-ultraviolet light. This paper reviews the red-light-emitting europium complexes with β-diketone and organic carboxylic acid as ligands that have been studied over the last five years, describes the current problems, and discusses their future application prospects. Full article

Curcumin (CU, turmeric), a polyphenolic phytochemical that is largely used as a food spice, has benefits for human health, which have led to increased interest in its therapeutic applications and its analysis from different matrices. The two guaiacol moieties of CU are responsible for its antioxidant properties and allow for its voltammetric quantification. Cyclic and differential pulse voltammetry (DPV) investigations at a single-use pencil graphite electrode (PGE) emphasized complex pH-dependent electrode processes, involving an equal number of protons and electrons. Theoretical calculations predicted a folded geometry for the β-diketone CU conformers, which interact with the PGE surface, exposing the electroactive moieties of only one aromatic ring. The Gibbs energy variations of the structures involved in CU electro-oxidation and the theoretical electrochemical potential values were calculated. CU’s DPV cathodic peak intensity recorded at an HB-type PGE in 0.05 mol × L⁻¹ H₂SO₄ varied linearly in the range 5.00 × 10⁻⁸–5.00 × 10⁻⁶ mol × L⁻¹ CU. The method’s detection and quantification limits were 2.12 × 10⁻⁸ mol × L⁻¹ and 6.42 × 10⁻⁸ mol × L⁻¹, respectively. The practical applicability of the developed method, successfully tested by CU assessment in dietary supplements, provided a recovery of 99.28 ± 2.04%. Full article

Organic light-emitting diodes (OLEDs) based on phosphorescent materials are among the most promising technologies for displays and lightings. For red-emitting heteroleptic iridium complexes (HICs), vast and major research has been focused on the design and synthesis of cyclometalated ligands, while relatively little attention has been given to ancillary ligands which also play important roles in manipulating the optoelectronic and electroluminescent properties of HICs. Seven deep red-emitting HICs were designed and synthesized by systematically modifying the alkyl groups in β-diketone-type ancillary ligands. These HICs exhibited similar physical and optoelectronic properties, with OLED devices based on these materials achieving consistent emission peaks at 624 nm and CIE coordinates of (0.68, 0.32). Among the synthesized HICs, Ir(dmippiq)₂(dmeacac), featuring 3,7-dimethyl-4,6-nonanedione as the ancillary ligand, demonstrated the best OLED performance, achieving a champion external quantum efficiency (EQE) of 18.26%. This result highlights that engineering the alkyl groups in β-diketone ancillary ligands can significantly enhance device performance. Full article

A series of differently substituted β-enaminones 2a,b, 4a–i, 8a–d, and 9–13, their BF₂-β-ketoiminate complexes 5a–d, and BF₂-β-diketonate complexes 6a–d were prepared as model substrates for photochemical transformations. The attempted photochemical transformations of enaminones 2, 4, 8 and BF₂-β-ketoiminate complexes 5 failed. On the other hand, irradiation of mixtures of BF₂-β-diketonate complexes 6a–d and cycloalkanes with UV-A light (365 nm) gave the corresponding De Mayo reaction products 7a–f in 9–30% yields. The photochemical ring-expansion of acetyl tetralone-derived BF₂-complex 6d gave novel diannulated cyclooctane derivatives 7e and 7f, which would be difficult to obtain using conventional cyclization methods. Full article

Organic compounds with 1,3-diketone or 3-amino enone functional groups are extremely important as they can be converted into a plethora of carbo- or heterocyclic derivatives or can be used as ligands in the formation of metal complexes. Here, we have achieved the preparation of a series of non-symmetrical β-ketoenamines (O,N,N proligand) of the type (4-MeOC₆H₄)C(=O)CH=C(R)NH(Q) obtained through the Schiff base condensation of 1,3-diketones (1-anisoylacetone, 1-anisyl-3-(4-cyanophenyl)-1,3-propanedione, and 1-anisyl-3-(4,4,4-trifluorotolyl)-1,3-propanedione) functionalized with electron donor and electron-withdrawing substituents and 8-aminoquinoline (R = CH₃, 4-C₆H₄CN, 4-C₆H₄CF₃; Q = C₉H₇N). Schiff base ketoimines with a pendant quinolyl moiety were isolated as single regioisomers in yields of 22–56% and characterized with FT-IR, ¹H NMR, and UV-visible spectroscopy, as well as single-crystal X-ray crystallography, which allowed for the elucidation of the nature of the isolated regioisomers. The regioselectivity of the condensation of electronically unsymmetrical 1,3-diaryl-1,3-diketones with 8-aminoquinoline was studied by ¹H NMR, providing regioisomer ratios of ~3:1 and ~2:1 in the case of CN and CF₃ substituents, respectively. The electronic effects correlate well with the difference between the Hammett σ⁺ coefficients of the two para substituents on the aryl rings. Full article

The metallocenyl-containing β-diketonato rhodium(I) dicarbonyl complexes of [Rh(FcCOCHCOR)(CO)₂] where R = CF₃, 10; Fc = ferrocenyl = Fe^II(C₅H₅)(C₅H₄), 11; Rc = ruthenocenyl = Ru^II(C₅H₅)(C₅H₄), 12; and Oc = osmocenyl = Os^II(C₅H₅)(C₅H₄), 13 were synthesized. Complexes 10–13 were then subjected to an electrochemical study utilizing cyclic voltammetry (CV), square wave voltammetry (SWV), and linear sweep voltammetry (LSV) in the non-coordinating solvent/supporting electrolyte medium CH₂Cl₂/0.1 mol dm⁻³ [N(ⁿBu)₄][B(C₆F₅)₄]. The formal reduction potential for the electrochemical reversible Fc^0/+ couples in 10–13 was identified in the range 0.156 ≤ E^o′ ≤ 0.328 V while the electrochemically irreversible osmocenyl and ruthenocenyl oxidations were observed at peak anodic potentials of E_pa = 0.640 V and E_pa = 0.751 V, respectively. Resolution between the closely overlapping CV-determined Fc^0/+ and Rh^I/II couples was too poor for unambiguous measurement of the Rh^I/II redox potential, but square wave voltammetry allowed estimates of E^o′ (Rh^I/II) in the range 0.156 ≤ E^o′ ≤ 0.398 V. FT-IR spectroelectrochemistry confirmed the one-electron oxidation of Rh^I by the appearance of CO vibrational bands at stretching frequencies, which are associated with rhodium(II) and not rhodium(III). Cytotoxicity tests on 10 (IC₅₀ = 19.2 µM) showed it to be substantially less cytotoxic than the free β-diketone, FcCOCH₂COCF₃, and [Rh(FcCOCHCOCF₃)(cod)]. Full article

α- or 4-Substituted curcumin analogues are scarce. We describe herein the syntheses and crystal structures of the first α-halogenated curcumin derivatives: (1E,6E)-1,7-bis (4-hydroxy-3-methoxyphenyl)-4-bromo-5-hydroxy-1,3,6-heptatriene-3-one or (4-bromocurcumin) (1) and (1E,6E)-1,7-bis (4-hydroxy-3-methoxyphenyl)-4-chloro-5-hydroxy-1,3,6-heptatriene-3-one or (4-chlorocurcumin) (2). We note that the key step in the successful synthesis of the bromo-analog is the use of slightly acidic media to favor the diketo form of curcumin prior to carrying out the reaction. Both newly prepared compounds assume the keto–enol form in the solid state and crystallize in the monoclinic space group P2₁/c with four molecules in the unit cell each with slightly different dimensions. Inter- and intra- molecular hydrogen bonds were observed in the two structures. Most significant observed features were the inter-molecular O…O distances of 2.842 and 2.840 Å and intra-molecular O…O distances of 2.460 and 2.451 Å for bromo-or (1) and chloro- or (2) derivatives, respectively. No close halogen…halogen contacts were observed in either of the two structures. Both molecules are nearly planar with torsion angles of 0.54 and 1.16 °C between the planes of two terminal phenyl groups for (1) and (2), respectively. π-Stacks were observed in both structures with interplanar distances of 3.367 and 3.454 Å for the bromo- and chloro- compounds, respectively. Hirshfeld surface analysis confirms quantitively a picture of the inter- and intra-molecular interactions in both compounds compared with polymorph I (the most common form) of curcumin. UV–Vis absorption spectra are shifted to higher wavelengths with l_max of 475 and 477 nm for compounds 1 and 2, respectively, compared with 442 nm in dichloromethane solutions. The newly synthesized molecules will open the door for numerous possible synthetic modifications of the α-carbon to prepare valuable analogues of curcumin with more favorable solubility profiles. Full article

The series of iridium(III) complexes, [Ir(ppy)₂(RCOCHCOR′)], with R = CH₃ and R′ = CH₃ (1), Rc (2), and Fc (3), as well as R = Rc and R′ = Rc (4) or Fc (5), and R = R′ = Fc (6), ppy = 2-phenylpyridinyl, Fc = Fe^II(η⁵–C₅H₄)(η⁵–C₅H₅), and Rc = Ru^II(η⁵–C₅H₄)(η⁵–C₅H₅), has been investigated by single-crystal X-ray crystallography and X-ray photoelectron spectroscopy (XPS) supplemented by DFT calculations. Here, in the range of 3.74 ≤ Σχ_R ≤ 4.68, for Ir 4f, Ru 3d and 3p and N 1s orbitals, binding energies unexpectedly decreased with increasing Σχ_R (Σχ_R = the sum of Gordy group electronegativities of the R groups on β-diketonato ligands = a measure of electron density on atoms), while in Fe 2p orbitals, XPS binding energy, as expected, increased with increasing Σχ_R. Which trend direction prevails is a function of main quantum level, n = 1, 2, 3…, sub-quantum level (s, p, d, and f), initial state energies, and final state relaxation energies, and it may differ from compound series to compound series. Relations between DFT-calculated orbital energies and Σχ_R followed opposite trend directions than binding energy/Σχ_R trends. X-ray-induced decomposition of compounds was observed. The results confirmed good communication between molecular fragments. Lower binding energies of both the Ir 4f_7/2 and N 1s photoelectron lines are associated with shorter Ir-N bond lengths. Cytotoxic tests showed that 1 (IC₅₀ = 25.1 μM) and 3 (IC₅₀ = 37.8 μM) are less cytotoxic against HeLa cells than cisplatin (IC₅₀ = 1.1 μM), but more cytotoxic than the free β-diketone FcCOCH₂COCH₃ (IC₅₀ = 66.6 μM). Full article

Epidermal wax is strategically situated at the interface between plants and air; therefore, it plays a key role in plants’ interactions with their surroundings. It is also unstable and susceptible to light intensity. Hosta plants are shade-loving herbs with admirable flowers and leaves. Hosta ‘Halcyon’ and Hosta ensata F. Maek. are two species of Hosta with a glaucous and a glossy appearance, respectively. Light intensity can affect the composition of epicuticular wax on the leaf surface, which influences the leaf color phenotype and ornamental value. In this paper, the crystal micromorphology, content, and components of epicuticular wax on the leaves of two species of Hosta under different light conditions (10%-, 30%-, 50%-, 70%-, and 100%-intensity sunlight, relative light intensity (RLI)) have been studied using pot experiments. The results indicate that the epicuticular wax crystals of H. ‘Halcyon’ and H. ensata are tubular and platelet-like, respectively. The wax crystals of H. ‘Halcyon’ melted and formed a thick crust under 100% RLI, and those of H. ensata melted and formed a thick crust under 70% and 100% RLI conditions. The primary ingredients of the epicuticular wax of the two species of Hosta contained primary alcohols, alkanes, fatty acids, and esters; β-diketones were only detected in H. ‘Halcyon’. The quantity of epicuticular wax of H. ‘Halcyon’ reduced at first and then increased with an RLI increase, achieving its lowest value at 50% RLI, but that of H. ensata declined little by little. The amounts of C28 primary alcohols, C31 alkanes, and C18 fatty acids were significantly higher than those of other carbon atoms in the two genotypes of Hosta. The C31β-diketones content decreased with the increase in light intensity, which caused the white frost phenotype to gradually weaken in H. ‘Halcyon’. Full article

A novel approach for the α-alkylation of ketones was developed using Brønsted acid-catalyzed C-C bond cleavage. Both aromatic and aliphatic ketones reacted smoothly with 2-substituted 1,3-diphenylpropane-1,3-diones to afford α-alkylation products with high yields and with excellent regioselectivity, in which the 1,3-dicarbonyl group acted as a leaving group in the presence of the catalyst TfOH. Mechanism experiments showed that the β-C-C bond cleavage of diketone and the shift of the equilibrium towards the enol formation from ketone are driving forces that induce the desired products. Full article

Trace concentrations of dyes are often present in textile wastewater streams and present a serious environmental problem. Thus, these dyes must be removed from wastewater either by degradation or sequestration prior to discharge of the wastewater into the environment. Existing processes to remove these wastewater contaminants include the use of solid sorbents to sequester dyes or the use of biochemical or chemical methods of dye degradation. However, these processes typically generate their own waste products, are not necessarily rapid because of the low dye concentration, and often use expensive or non-recyclable sequestrants or reagents. This paper describes a simple, recyclable, liquid–liquid extraction scheme where ionic dyes can be sequestered into poly(α-olefin) (PAO) solvent systems. The partitioning of anionic and cationic dyes from water into PAOs is facilitated by ionic PAO-phase anchored sequestering agents that are readily prepared from commercially available vinyl-terminated polyisobutylene (PIB). This is accomplished by a sequence of reactions involving hydroboration/oxidation, conversion of an alcohol into an iodide, and conversion of the resulting primary alkyl iodide into a cationic nitrogen derivative. The products of this synthetic sequence are cationic nitrogen iodide salts which serve as anionic sequestrants that are soluble in PAO. These studies showed that the resulting series of cationic PIB-bound cationic sequestering agents facilitated efficient extraction of anionic, azo, phthalein, and sulfonephthalein dyes from water into a hydrocarbon PAO phase. Since the hydrocarbon PAO phase is completely immiscible with water and the PIB derivatives are also insoluble in water, neither the sequestration solvent nor the sequestrants contaminate wastewater. The effectiveness and efficiency of these sequestrations were assayed by UV–visible spectroscopy. These spectroscopic studies showed that extraction efficiencies were in most cases >99%. These studies also involved procedures that allowed for the regeneration and recycling of these PAO sequestration systems. This allowed us to recycle the PAO solvent system for at least 10 sequential batch extractions where we sequestered sodium salts of methyl red and 4′,5′-dichlorofluorescein dyes from water with extraction efficiencies of >99%. These studies also showed that a PIB-bound derivative of the sodium salt of 1,1,1-trifluoromethylpentane-2,4-dione could be prepared from a PIB-bound carboxylic acid ester by a Claisen-like reaction and that the sodium salt of this β-diketone could be used to sequester cationic dyes from water. This PIB-bound anion rapidly and efficiently extracted >99% of methylene blue, malachite green, and safranine O from water based on UV–visible and ¹H NMR spectroscopic assays. Full article