Platinum(II) complexes with pyridyl azolate-based chelates: synthesis, structural characterization, and tuning of photo- and electrophosphorescence

A new series of luminescent platinum(II) azolate complexes with a formula of [Pt(NwedgeN)(2)], in which NwedgeN = mppz (1), bppz (2a), bzpz (2b), bmpz (2c), bqpz (2d), fppz (3a), hppz (3b), bptz (4), hptz (5), were synthesized, and their photophyscial properties were examined. Single-crystal X-ray diffraction studies of 2c and 3b revealed a planar molecular geometry, in which the NwedgeN chelates adopt a trans configuration and show notable interligand C-H...N hydrogen bonding within the complex. Interesting intermolecular interactions were observed in the solid state. Complex 2c formed a slipped-stack structure with a Pt...Pt separation distance of 6.432 Angstroms, while complex 3b showed a columnar stacking with the molecules oriented in an alternating order in relation to the chain axis, giving a much reduced Pt...Pt distance of 3.442 Angstroms. The lowest absorption band for all complexes revealed strong state mixings between the singlet and triplet (MLCT and intraligand pipi) manifolds. Complexes 1 and 2 showed mixed (3)MLCT and (3)pipi phosphorescence in fluid solution. While radiationless deactivation was apparently dominant for complexes 3-5 in solution, resulting in rather weak emission, strong phosphorescence was observed in the room-temperature solid state with the peak wavelength being significantly red shifted compared to that in solution. The emission nature has been tentatively assigned to be (3)MMLCT in character. OLED devices with a multilayer configuration of ITO/NPB/CBP:2a/BCP/Alq(3)/LiF/Al were successfully fabricated using a CBP layer doped with various amount of 2a, ranging from 6 to 100%, as the emitting layer. A substantial red shift with increasing doping concentrations was observed in electroluminescence. With a neat film of 2a, the device showed a green emission with lambda(max) at 556 nm and an external QE of approximately 1.6% at a driving current of 20 mA. Similarly, for the device using a neat film of 3a, an electroluminescence centered at 616 nm with a slightly reduced external QE of approximately 2.1% was recorded. Aggregation of platinum(II) complexes in the solid state was proposed to account for the large red-shift in electroluminescence.     

Strobovideolaryngoscopic Findings in Singing Teachers

Professional voice users often present to otolaryngologists and laryngologists with specific voice complaints. The contributions of pathologic lesions to the patients' vocal complaints are not always clear on examination, and often, premorbid examinations of the larynx are not available for review. This study examines the incidence of laryngeal pathology among singing teachers. At a national convention of singing teachers, volunteers were recruited for a "free strobovideolaryngoscopic examination." All volunteers completed a detailed questionnaire of their vocal and medical history and underwent strobovideolaryngoscopic examination. Strobovideolaryngoscopic examinations were completed in 20 volunteers, 7 of whom had voice complaints and 13 of whom perceived their voices to be normal. Vocal fold masses were common among the asymptomatic singing teachers. Evidence of reflux laryngitis was a common finding among both symptomatic and asymptomatic singing teachers. Asymmetries in vocal fold hypomobility were more common among those with voice complaints than was the presence of vocal fold masses in the population studied.     

A synergistic organoiron flame-retarding/smoke-suppressing system for ABS

Commercial acrylonitrile butadiene styrene (ABS) polymers are among the most flammable of the currently available range of thermoplastic materials. In addition to having a rather low limiting oxygen index (LOI) value in the range 18.3–18.8, ABS polymers also produce compious amounts of smoke and hazardous gases when burnign in the air. In a recent study directed towards preparing and evaluating compounds which would simultaneously reduce the flammability and smoke produced from burning thermoplastic polymers, a synergistic flame-retarding/smoke-suppressing system based on organoiron compounds has been produced, which when properly compounded into ABS/PVC [poly(vinyl chloride)] blends more than doubles the LOI nad at the same time reduces smoke production significantly.     

Fluorinated aminoalkoxide and ketoiminate indium complexes as MOCVD precursors for In2O3 thin film deposition

The syntheses of two distinctive types of indium complex derived from trimethylindium (InMe(3)) are reported. The first kind has a generalized structural formula [InMe(2)(amak)](2), where (amak)H is an abbreviation for a series of chelating amino alcohol ligands HOC(CF(3))(2)CH(2)NHR, R = (CH(2))(2)OMe (1), Me (2), and Bu(t) (3), as well as HOC(CF(3))(2)CH(2)NMe(2) (4); while the second type of complex is illustrated by [InMe(2)(keim)] (5), for which (keim)H is a tridentate ketoimine ligand of structural formula O=C(CF(3))CH(2)C(CF(3))=NCH(2)CH(2)NMe(2). The solid-state structures of 2 and 5 were determined using single crystal X-ray diffraction studies. For the aminoalkoxide complexes 2-4, the existence of dimeric In(2)O(2) core structures in the solid state has been established with the amino fragment located trans to the alkoxide ligands, in a molecular arrangement which is in contrast to the distorted, trigonal bipyramidal geometry observed for the ketoiminate complex 5. Moreover, VT NMR studies of 2 revealed a rapid dimer-to-monomer equilibration and simultaneous rupture of the N-->In dative interaction, affording two interconvertible isomers related by having the N-Me substituents in either trans or cis dispositions. For complexes 2 and 5, deposition of In(2)O(3) thin films was successfully conducted at temperatures 400-500 degrees C, using O(2) as the carrier gas to induce indium oxide deposition and to suppress carbon impurity present in the thin film. Scanning electron micrographs (SEMs) revealed the surface morphologies. The atomic composition of these films was examined by both X-ray photoelectron spectroscopy (XPS) and Rutherford backscattering (RBS) methods, while X-ray diffraction studies (XRD) confirmed the formation of a preferred orientation along the (222) planes.     

Erratum

An X-ray structural study of the trinuclear complex Fe₃(CO)₇[Pn₂PC₄(CF₃)₂ PPh₂ (I) has shown that the conversion of another trinuclear complex Fe₃(CO)₈[Ph₂PC₄(CF₃)₂]PPh₂ (II) to (I) involves intramolecular CO elimination, metalmetal bond formation and novel structural changes in a diphenylphosphide bridge.