Novel yellow phosphorescent iridium complexes containing a carbazole–oxadiazole unit used in polymeric light-emitting diodes

Yellow iridium complexes Ir(PPOHC)₃ and (PPOHC)₂Ir(acac) (PPOHC: 3-(5-(4-(pyridin-2-yl)phenyl)-1,3,4-oxadiazol-2-yl)-9-hexyl-9H-carbazole) were synthesized and characterized. The Ir(PPOHC)₃ complex has good thermal stability with 5% weight-reduction occurring at 370 °C and a glass-transition temperature of 201 °C. A polymeric light-emitting diode using the Ir(PPOHC)₃ complex as a phosphorescent dopant showed a luminance efficiency of 16.4 cd/A and the maximum external quantum efficiency of 6.6% with CIE coordinates of (0.50, 0.49). A white polymeric light-emitting diode was fabricated using Ir(PPOHC)₃ which showed a luminance efficiency of 15.3 cd/A, with CIE coordinates of (0.39, 0.44). These results indicate that the iridium complexes containing a linked carbazole–oxadiazole unit are promising candidates in high-efficiency electroluminescent devices.     

Novel yellow phosphorescent iridium complexes containing a carbazole-oxadiazole unit used in polymeric light-emitting diodes

Yellow iridium complexes Ir(PPOHC)₃ and (PPOHC)₂Ir(acac) (PPOHC: 3-(5-(4-(pyridin-2-yl)phenyl)-1,3,4-oxadiazol-2-yl)-9-hexyl-9H-carbazole) were synthesized and characterized. The Ir(PPOHC)₃ complex has good thermal stability with 5% weight-reduction occurring at 370 °C and a glass-transition temperature of 201 °C. A polymeric light-emitting diode using the Ir(PPOHC)₃ complex as a phosphorescent dopant showed a luminance efficiency of 16.4 cd/A and the maximum external quantum efficiency of 6.6% with CIE coordinates of (0.50, 0.49). A white polymeric light-emitting diode was fabricated using Ir(PPOHC)₃ which showed a luminance efficiency of 15.3 cd/A, with CIE coordinates of (0.39, 0.44). These results indicate that the iridium complexes containing a linked carbazole-oxadiazole unit are promising candidates in high-efficiency electroluminescent devices.     

A new family of trinuclear Ru(II) polypyridyl complexes acting as pH-induced fluorescence switch

Tripodal ligands 1,3,5-tris{4-((1,10-phenanthroline-[5,6-d]imidazol-2-yl)phenoxy)methyl}-2,4,6-trimethylbenzene (L¹), 1,1,1-tris{4-((1,10-phenanthroline-[5,6-d]imidazol-2-yl)phenoxy)methyl}propane (L²), 2,2′,2′′-tris{4-((1,10-phenanthroline-[5,6-d]imidazol-2-yl)phenoxy)ethyl}amine (L³), and corresponding Ru(II) complexes [(bpy)₆L^1–3(Ru^II)₃](PF₆)₆, shortly called (Ru–L^1–3), have been synthesized. UV–vis absorption and fluorescence spectra of these complexes are both strongly dependent on the pH of the buffer solution. These complexes act as pH-induced off–on–off fluorescence switch through protonation and deprotonation of the imidazole-containing ligands.     

Four new cyclometalated phenylisoquinoline-based Ir(III) complexes: Syntheses,structures, properties and DFT calculations

Four new cyclometalated phenylisoquinoline-based iridium(III) complexes [Ir(C^∧N)₂(bipy)]PF₆ (5a–5d) (bipy = 2,2′-bipyridine) have been synthesized and fully characterized, where the C^∧N ligands are 1-(4-(trifluoromethyl)phenyl)isoquinoline, 4-(isoquinolin-1-yl)benzaldehyde, 4-(isoquinolin-1-yl)benzonitrile and 1-(3-fluoro-4-methylphenyl)isoquinoline, respectively. The crystal structures of 5a and 5c have been determined. The photophysical and electrochemical properties of these new complexes 5a–5d have been studied. All Ir(III) complexes exhibit orange phosphorescence in dichloromethane solution at room temperature with a maximum at 593–618 nm, quantum yield of 0.046–0.16. The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 5a–5d have been calculated with density functional theory (DFT) and time-dependent DFT (TD-DFT).     

Ring-opening copolymerization of CHO and MA catalyzed by the asymmetrical Cr(III)-bis-Schiff-base complex

Using an asymmetrical Cr(III)-bis-Schiff-base complex [Cr(L)Cl] (1; H₂L obtained from condensation of 5-bromo-salicylaldehyde and HL⁰ ((Z)-4-((2-aminophenylimino)(phenyl)methyl)-3-methyl-1H-pyrazol-5(4H)-one) as the catalyst, bulk solvent-free ring-opening copolymerization of CHO (cyclohexene oxide) and MA (maleic anhydride) in the presence of cocatalyst DMAP (4-(dimethylamino)-pyridine) was effectively realized, in which, on the condition of low 1/DMAP concentration for a controllable polymerization, perfectly alternating polyester while not poly(ester-co-ether) could be obtained.     

Coordination of a Schiff base as an iminium-phenone zwitterion in a double ligand-bridged fac-[Re(CO)3]+ dimer

The ligand-bridged dimers [Re(CO)₃(μ-H₂salet)]₂ (1) and [{Re(CO)₃}₂(μ-salpd)] (2) are formed by the reactions of [Re(CO)₅Cl] with the potentially heptadentate Schiff base 2,2′,2″-tris(salicylideneimino)triethylamine (H₃salet) and the hexadentate N¹-(3-(2-hydroxybenzylidene-amino)propylamino)ethyl)-benzylidenepropane-1,3-diamine (H₂salpd) respectively. In 1, the two H₂salet ligands bridge two fac-[Re(CO)₃]⁺ moieties. Mono-dentate coordination is by a neutral phenone oxygen atom, generated by the conversion of one salicylideneimine entity to an iminium zwitter-ion. In 2 each fac-[Re(CO)₃]⁺ core resides in a ‘3 + 0’ environment. In both complexes π–π interaction between the phenolate rings contribute to the stability. The crystal structures of 1 and 2 were determined by X-ray single crystal diffraction. Spectroscopic results are also reported.     

Rhenium(I) complexes with aliphatic Schiff bases appended to bio-active moieties

Novel facial tricarbonylrhenium(I) complexes, fac-[Re(urca)₂(CO)₃Cl] (1) and fac-[Re(bzta)(CO)₃Cl] (2) were isolated from the coordination reactions of 5-((5-hydroxypentylimino)methyl)uracil (urca) and 2-((5-hydroxypentylimino)methyl)benzothiazole (bzta) with [Re(CO)₅Cl], respectively. Spectral characterization of metal complexes 1 and 2 were supported by their X-ray crystal structures. DNA interactions were assessed via UV–Vis calf-thymus (CT)-DNA binding titrations and gel electrophoresis. Redox properties of the metal complexes were probed using voltammetry.     

[18F]PRIMATX,a New Positron Emission Tomography Tracer for Imaging of Autotaxin in Lung Tissue and Tumor-Bearing Mice

Autotaxin (ATX) is a secreted enzyme with tissue levels associated with tissue injury, which increase during wound healing and chronic fibrotic diseases. We selected [¹⁸F](R,E)-3-(4-chloro-2-((5-methyl-2H-tetrazol-2-yl)methyl)phenyl)-1-(4-((5-(2-fluoroethoxy)pyridin-2-yl)methyl)-2-methylpiperazin-1-yl)prop-2-en-1-one ([¹⁸F]PRIMATX, [¹⁸F] 2 ), a tracer for positron emission tomography, to image ATX expression in vivo. It successfully differentiates expression levels in lung tissue samples from idiopathic pulmonary fibrosis patients, and allows the detection of ATX-expressing tumors in living mice, confirming its potential for development as a clinical imaging agent.     

A New Multifunctional Triazine?Carbazole Compound with High Triplet Energy for High-Performance Blue Fluorescence,Green and Red Phosphorescent Host,and Hybrid White Organic Light-Emitting Diodes

A blue fluorescent compound, 9-[4-(4,6-diphenoxy-1,3,5-triazin-2-yl)phenyl]-9H-carbazole (POTC), the triplet energy level of which reaches 2.76 eV, has been designed and synthesized. POTC is an excellent blue emitter as well as host for green and red phosphors, and therefore, matches the requirements of the host for single-emitting-layer fluorescence and phosphorescence hybrid white organic light-emitting diodes (OLEDs). The blue, green, red, and white devices based on POTC show maximum external quantum efficiencies (EQEs) of 2.4, 22.4, 13.0, and 8.1 %, respectively. Even at a high brightness of 1000 cd m⁻², these values maintain EQEs of 2.3, 22.1, 11.1, and 7.0 %, respectively, indicating less than 15 % roll-offs from the maxima.     

In situ synthesis and dielectric properties of copper(II) and nickel(II) chiral Schiff base complexes

Two chiral Schiff base-containing complexes, [Cu(L¹)](ClO₄)₂·H₂O (1, L¹ = (S,S)-N1,N2-bis((1H-imidazol-4-yl)methylene)cyclohexane-1,2-diamine) and [Ni(L²)₂](ClO₄)₂ (2, L² = (S,S)-N1-((1H-imidazol-4-yl)methylene)cyclohexane-1,2-diamine) were synthesized from the reaction mixture of 1H-imidazole-4-carbaldehyde, (S,S)-1,2-diaminocyclohexane and Cu(ClO₄)₂·6H₂O or Ni(ClO₄)₂·6H₂O in methanol. Single-crystal X-ray diffraction analyses reveal that the in situ generated chiral Schiff base ligands L¹ and L² are bisubstituted and monosubstituted, respectively, corresponding to the different metal ions Cu^II and Ni^II. Variable-frequency and -temperature dielectric properties of 1 and 2 have been studied.     

Exploring the Molecular Mechanisms Underlying the in vitro Anticancer Effects of Multitarget-Directed Hydrazone Ruthenium(II)–Arene Complexes

The molecular targets and the modes of action behind the cytotoxicity of two structurally established N,O- or N,N-hydrazone ruthenium(II)–arene complexes were explored in human breast adenocarcinoma cells (MCF-7) and paralleled in non-cancerous and cisplatin-resistant counterparts (MCF-10A and MCF-7CR respectively). Both complexes, [Ru(hmb)(L1)Cl] ( 1 , L1=4-((2-(2,4-dinitrophenyl)hydrazono)(phenyl)methyl)-3-methyl-1-phenyl-1H-pyrazol-5-olate) and [Ru(cym)(L2)Cl] ( 2 , L2=1-((3-methyl-5-oxo-1-phenyl-1H-pyrazol-4(5H)-ylidene)(phenyl)methyl)-2-(pyridin-2-yl)hydrazin-1-ide), reversibly interact with moderate-to-high affinity with a number of molecular targets in cell-free assays, namely serum albumin, DNA, the 20S proteasome and hydroxymethylglutaryl-CoA reductase. Most interestingly, only 2 readily crosses the cell membrane and preserves its binding/modulatory ability toward the targets of interest upon rapid cellular internalization. The resulting action at multiple levels of the cancer cascade is likely the cause for the selective sensitization of tumour cells to p27-mediated apoptotic death, and for the ability of 2 to overcome the drug resistance problem.     

Synthesis and characterization of Cu(I) and Zn(II) complexes with new sulfur-bearing isoxazole- or pyrazole-based ligands

The synthesis of the new ligands 6-(5-methyl-1,2-oxazol-3-yl)-2,3-dihydro-5H-[1,4] dithiino[2,3-c]pyrrole-5,7(6H)-dione (isox′) and 6-(3-methyl-1H-pyrazol-5-yl)-2,3-dihydro-5H-[1,4]dithiino[2,3-c]pyrrole-5,7(6H)-dione (pyraz′) and their coordination chemistry toward Cu(I) and Zn(II), was studied. The ligands and their complexes were characterized using a combination of either multinuclear NMR (¹H and ¹³C{¹H}), HRMS, FTIR or Uv–Vis spectroscopy. The solid state structures of ligand isox′ and complexes [Cu(pyraz′)₂]OTf and [Zn(OOCCF₃)₂(pyraz′)₂] were determined. Interestingly, isox′ presents a yellow luminescence in its free form. Additionally, the ability of isox′ to coordinate as an N–O bidentate ligand or as an N–S bridge between two copper centers, forming a coordination polymer, is studied. The solid state structure of this Cu(I)-isox′ 1D coordination polymer is also reported.     

Preparation and characterization of a novel host (zeolite NaY)/guest (copper(II) complex of a new bidentate Schiff base ligand) nanocomposite material (HGNM): a comparison between catalytic reactivity of free and encapsulated complexes in oxidation of benzyl alcohol and aldol condensation

A copper(II) complex of 4-((E)-(4-(1H-benzo[d]imidazol-2-yl)phenyl)diazenyl)-2-((E)-(4-hydroxyphenylimino) methyl)phenol (HL) was encapsulated in zeolite NaY by flexible ligand method. The structure of encapsulated complex was characterized by spectroscopic (electronic and FT-IR), XRD, TGA, BET and elemental analysis data. Furthermore, catalytic activity of the neat and encapsulated complexes was studied in oxidation of benzyl alcohol and aldol condensation. The encapsulated complex was more reactive and stable than the corresponding free complex. Nanocomposite material was enough stable to be reused for several times. Finally, the reaction parameters were optimized for oxidation of benzyl alcohol and aldol condensation.     

Novel fluoranthene dyes for efficient dye-sensitized solar cells

Three, novel, fluoranthene-based dyes, 2-cyano-3-(5-(7,12-diphenylbenzo[k]fluoranthen-3-yl)thiophen-2-yl)acrylic acid, 2-(5-((5-(7,12-diphenylben-zo[k]fluoranthen-3-yl)thiophen-2-yl)methylene)-4-oxo-2-thioxothiazolidin-3-yl)acetic acid and 2-cyano-3-(4-(2-(7,12-diphenylbenzo[k]fluoranthen-3-yl)ethynyl) phenyl) acrylic acid, were synthesized for application as sensitizers in dye-sensitized solar cells. In each dye, the 7,12-diphenyl-benzo[k]fluoranthene moiety acted as electron donor with phenyl and thiophene units as electron spacers and carboxylic acid as electron acceptor. Tuning of the HOMO and LUMO energy levels was conveniently accomplished by changing the spacer and acceptor moiety, as confirmed using electrochemical measurements. Maximum solar energy:electricity conversion efficiency was 4.4% under AM 1.5 solar simulator (100 mW cm^?2) for 2-cyano-3-(5-(7,12-diphenylbenzo[k]fluoranthen-3-yl)thiophen-2-yl)acrylic acid. The results suggest that dyes based on fluoranthene donor are promising candidates for high performance, dye-sensitized solar cells.     

Toward chiral iron(II) spin-crossover grafted resins with imidazole Schiff-base ligands

Using chiral imidazole Schiff-base as ligands, two couples of mononuclear iron(II) enantiomeric complexes fac-Λ-[Fe(R-L)₃](ClO₄)₂·H₂O (1), fac-Δ-[Fe(S-L)₃](ClO₄)₂·H₂O (2), fac-Λ-[Fe(R-L)₃](BF₄)₂·H₂O (3), fac-Δ-[Fe(S-L)₃](BF₄)₂·H₂O (4) (L = 1-(2-naphthyl)-N-((1-methyl-imidazol-2-yl)methylene)ethanamine) have been successfully synthesized and characterized. The CD spectra of 1 and 2, 3 and 4, were basically mirror images confirming their enantiomers. X-ray crystallography revealed that complexes 1–4 all crystallized in the chiral space group P2₁3 with the iron(II) center surrounded by three bidentate ligands. Magnetic measurements revealed incomplete spin transition for 1, and gradual spin crossover (T_1/2 = 150 K) for 3. However, the spin-crossover behaviors were vanished after grafting 1–4 to the Merrifield's peptide resin, and the iron(II) centers in the resin remained in a high-spin state in the temperature range of 2–300 K.     

Monomeric complexes of Re(CO)3+ ion with tridentate N∩N∩O−ligands — Schiff base derivatives of salicylic aldehyde

Simple synthetic procedures, reactions of Re(CO)₅Cl with potentially tridentate N∩N∩OH ligands (Schiff bases prepared from aliphatic or aromatic amines and salicylic aldehyde) lead to formation of monomeric complexes of fac-Re(CO)₃⁺ ion. Three obtained complexes have been characterized by means of elemental analyses and IR, UV–vis, and EI-MS techniques. Molecular structures of the synthesized species were investigated using X-ray diffraction measurements. Depending on the nature of N∩N∩OH ligand the investigated Schiff bases form with fac-Re(CO)₃⁺ ion bidentate or tridentate chelates with N∩N, N∩O⁻ or N∩N∩O⁻ coordination types.     

Two-photon absorption dyes with thiophene as π electron bridge: Synthesis, photophysical properties and optical data storage

Four novel dyes are prepared by thiophene as π bridge between carbazole central core and other terminal groups by Suzuki and Heck coupling reactions. These dyes are fully characterized by IR, ¹H NMR, ¹³C NMR, MS and elemental analysis. Linear absorption, single- and two-photon excited fluorescence in various solvents are experimentally investigated. The calculated two-photon absorption cross sections of 9-Hexyl-3,6-di((5-phenyl)-2-thienyl)carbazole (1), 9-Hexyl-3,6-di((5-thienyl)-2-thienyl)carbazole (2), 9-Hexyl-3,6-di((5-p-vinylpyridyl)-2-thienyl)-carbazole (3) and 9-Hexyl-3,6-di-((5-o-vinylpyridyl)-2-thienyl)carbazole (4) for the lowest excited state are 537.84, 550.76, 1292.95 and 1340.40 × 10⁻⁵⁰ cm⁴ s photon⁻¹, respectively. Calculated and experimental data have shown that thiophene as π electron bridge improves the two-photon absorption cross sections greatly. Two-photon optical data recording experiments have been carried out at 820 nm laser radiation.     

Novel carbazole/pyridine-based host material for solution-processed blue phosphorescent organic light-emitting devices

3,6-Bis(3,5-di(pyridin-3-yl)phenyl)-9-phenyl-9H-carbazole, a novel host material for solution-processed blue phosphorescent organic light-emitting devices was synthesized by a Suzuki coupling reaction. The optical, electrochemical and thermal properties of this novel crabazole have been characterized. The compound exhibits a high glass-transition temperature (Tg = 161 °C) and high triplet energy (E_T = 2.76 eV). Additionally, atomic force microscopy measurements indicate that high-quality amorphous films of this novel compound can be prepared by spin-coating. Solution-processed blue phosphorescent organic light-emitting devices were obtained using the carbazole as the host material for the phosphorescence emitter iridium(III) bis(4,6-difluorophenylpyridinato)- picolinate and their electroluminescence properties were evaluated.     

A rhenium(I) compound bearing a dimerized chromone NO bidentate chelator

Herein, we communicate the synthesis of a novel rhenium(I) complex, fac-[Re(CO)₃(chrpychr)Br] (1) from the equimolar reaction between 2-(4-oxo-4H-chromen-3-yl)-5H-chromeno[2,3-d]pyrimidin-5-one (chrpychr) and [Re(CO)₅Br]. The metal complex 1 was characterized via ¹H NMR-, IR- and UV–Vis spectroscopy and conductivity measurements. Single crystal X-ray analysis provides definitive confirmation in the structural elucidation of 1. DFT studies of 1 aided in the interpretation of its experimental IR spectrum.