Bis-tridentate IrIII Phosphors Bearing Two Fused Five-Six-Membered Metallacycles: A Strategy to Improved Photostability of Blue Emitters

Iridium complexes bearing chelating cyclometalates are popular choices as dopant emitters in the fabrication of organic light-emitting diodes (OLEDs). In this contribution, we report a series of blue-emitting, bis-tridentate Ir^III complexes bearing chelates with two fused five-six-membered metallacycles, which are in sharp contrast to the traditional designs of tridentate chelates that form the alternative, fused five-five metallacycles. Five Ir^III complexes, Px-21 – 23 , Cz-4 , and Cz-5 , have been synthesized that contain a coordinated dicarbene pincer chelate incorporating a methylene spacer and a dianionic chromophoric chelate possessing either a phenoxy or carbazolyl appendage to tune the coordination arrangement. All these tridentate chelates afford peripheral ligand–metal–ligand bite angles of 166–170°, which are larger than the typical bite angle of 153–155° observed for their five-five-coordinated tridentate counterparts, thereby leading to reduced geometrical distortion in the octahedral frameworks. Photophysical measurements and TD-DFT studies verified the inherent transition characteristics that give rise to high emission efficiency, and photodegradation experiments confirmed the improved stability in comparison with the benchmark fac-[Ir(ppy)₃] in degassed toluene at room temperature. Phosphorescent OLED devices were also fabricated, among which the carbazolyl-functionalized emitter Cz-5 exhibited the best performance among all the studied bis-tridentate phosphors, showing a maximum external quantum efficiency (EQE_max) of 18.7 % and CIE_x,y coordinates of (0.145, 0.218), with a slightly reduced EQE of 13.7 % at 100 cd m⁻² due to efficiency roll-off.     

Spectrophotometric analysis, thermal analysis and gravimetric determination of some metal ions with oxime and Schiff's base derivatives of N-furoylphenylhydroxylamine

The oxime and Schiff's base of N-furoylphenylhydroxylamine form complexes with Co²⁺, Cu²⁺, Zn²⁺ and Fe³⁺. These complexes were studied by means of the UV — Vis. spectra of nujol mulls, electron spin resonance (ESR) spectra and magnetic susceptibility to determine their stereochemistry. The complexes were characterized via elemental analyses, molar conductivities and thermogravimetric analyses. Organic reagents were used for the gravimetric determination of Co²⁺, Cu²⁺ and Fe³⁺ through the precipitation of their complexes. The compounds were also used for separation of a binary mixture of Cu²⁺ and Cu²⁺. Interferences were studied.     

Alkyl 3-amino-5-aryl-2-benzoyl-5-oxo-2-pentenoates as new chelating ligands and reagents of heterocyclic synthesis

A method for the synthesis of alkyl 3-amino-5-aryl-2-benzoyl-5-oxo-2-pentenoates from Ni chelates of alkyl benzoylacetates and aroylacetonitriles was proposed. The compounds obtained were used for preparation of ethyl 4-amino-6-aryl-2-phenylnicotinates and Ni and B chelates.     

Thermal behaviour of polyacrylamidoxime-copper chelates

The purpose of this work was to investigate the effect of several factors (anion type in the copper salt, pH and concentration of the salt solution) on the structure and thermo-oxidative degradation of the polyacrylamidoxime-copper chelates, by using elemental analysis, IR spectroscopy and dynamic thermogravimetry. The chelates containing copper ions as sulphate exhibit a better initial thermal stability than the polyacrylamidoxime fibre presumably due to the crosslinking generated by the intermolecular complexation of the ions; the removal of the sulphate anions takes place concomitantly with the second step of polymeric chain decomposition. The initial thermal decomposition of the chelates formed by copper ions as nitrate begins at lower temperatures as compared to the polyacrylamidoxime fibre, probably by the nitrate anion release, which partly overlaps the initial decomposition of the copper ion-crosslinked polymeric chains. Copper ions as either sulphate or nitrate catalyse the reactions involved in the main step of polyacrylamidoxime fibre decomposition; the higher the copper amount, the stronger the catalytic effect.     

Kinetics of formation of a linear polymer-polymer network system in the presence of 3d metal chelates

For semi-interpenetrating polymer networks (semi-IPNs) based on an incompatible polyurethane network/linear polymethylmethacrylate pair formed in situ in the presence of 3d metal chelates, we have studied the effect of the system composition on the kinetics of formation of the components and the nature of complex formation between the metal compound and the polymer matrix. The ratio of the system components has been shown to have an effect on the selection of the macroligand in formation of complexes of the metal chelate with the polar groups of the semi-IPN, where the general character of the kinetic behavior for the formation of the network and the linear polymer is preserved. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 351–356, November–December, 2006.     

Borchelate und Bormetallchelate, 4. Mitt.

The i.r., u. v.,¹H n.m.r.,¹³C n.m.r., and¹¹B n.m.r. spectra of several substituted diphenylboron chelates derived from salicylaldehyde azomethines were compared with respect to the influence of the amine substituentR. O–B–N-6-ring constitution of the chelates29–32 [R=OH, NH₂, NHC₆H₅, N(CH₃)₂] can be deduced from the spectra.

Als 3. Mitt. gilt:F. Umland undE. Hohaus mit Beiträgen vonW. Riepe, K. Brodte, C. Schleyerbach undD. Szonn. Untersuchungen über borhaltige Ringsysteme vom Chelattyp. Forschungsbericht des Landes Nordrhein-Westfalen Nr. 2538. Opladen: Westdeutscher Verlag. 1976.     

Ethyl 3,3-diamino-2-(2-p-tolylpyrimidin-4-yl)acrylate,a new representative of hetarylketene aminals

A new representative of hetarylketene aminals, ethyl 3,3-diamino-2-(2-p-tolylpyrimidin-4-yl)acrylate, was synthesized by the reaction ofp-toluamidine with the condensation product of dimethylformamide dimethyl acetal and the difluoroboron chelate of acetyl(ethoxycarbonyl)ketene (N-benzoyl)aminal. This synthesis is an example of pyrimidine ring assembly using the methodology based on transformations of chelate complexes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1638–1640, September, 1994.This research was partially supported by the International Science Foundation (Grant No. M5QOOO).     

Stereoselective adduct formation of α-acylcamphorato-copper(II) chelates with some chiral Lewis bases

The formation constants of the mono-adducts of α-acylcamphorato-copper(II) chelates such as (+)-Cu(facam)₂, (?)-Cu(facam)₂, (+)-Cu(hfbc)₂ and (?)-Cu(hfbc)₂ with some chiral Lewis bases were determined spectrophotometrically in benzene. In order to compare the adduct formation constants obtained with the (+)- and (?)-forms, some pairs of chiral Lewis bases such as 1-amino-2-propanol [(R)(?), (S)(+)], 1-(α-naphthyl)ethylamine [(R)(+), (S)(?)], α-phenyl ethylamine [(R)(+), (S)(?)] and also quinine and quinidine were examined as neutral ligands. Although not very pronounced, the effects of combinations obtained for (+)- or (?)-Cu(II) chelates and (+)- or (?)-ligands indicate that formation constants obtained by the formation of adducts with the ligands having different directions of the optical rotation seems to be superior to those with the same direction.     

过渡金属乙酰丙酮螯合物的体积排除色谱研究

用定量体积排除色谱方法研究了过渡金属Fe(Ⅲ)、Co(Ⅲ)、Cu(Ⅱ)、Ni(Ⅱ)的乙酰丙酮螯合物在四氢呋喃溶液中的加合和缔合行为。在溶液中乙酰丙酮钴(Ⅲ)以单个螯合物分子的形式存在,乙酰丙酮铜(Ⅱ)和乙酰丙酮铁(Ⅲ)与溶剂加合生成加合物,乙酰丙酮铁(Ⅲ)除加合物外还存在缔合度为2-10的多分散缔合物,乙酰丙酮镍(Ⅱ)水合物在四氢呋喃中产生了加合交换作用,同时存在缔合度为6左右的缔合物。色谱数据给出了螯合物、加合物及缔合物     

Chelate synthesis of 2,2′-bipyridin-4-one

A method for the synthesis of 2,2′-bipyridin-4-one from 4-amino-4-(2-pyridyl)-but-3-en-2-onevia its diphenylboron, chelates was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2071–2073, November, 1997.