We report the synthesis and characterization of a neutral heteroleptic Ir(III) complex bearing 6-fluoro-2-phenylbenzo[d]thiazole as cyclometalating ligand and (Z)-6-(9H-carbazol-9-yl)-5-hydroxy-2,2-dimethylhex-4-en-3-one as ancillary ligand. The photodeactivation mechanisms have been elucidated through extensive density functional theory (DFT) calculations. The active role of metal-centered ((3) MC) triplet excited states in the nonradiative deactivation pathways is, for first time, confirmed in such complexes.
View Article and Find Full Text PDFThe synthesis, photophysical properties and application as emitters in solution-processed multi-layer organic light-emitting diodes (OLEDs) of a series of blue-green to red light-emitting phosphorescent platinum(II) complexes are reported. These complexes consist of phenylisoquinoline, substituted phenylpyridines or tetrahydroquinolines as C^N cyclometalating ligands and dipivaloylmethane as an ancillary ligand. Depending on both the structure of the C^N cyclometalating ligands and the dopant concentration in the matrix, these platinum(II) complexes exhibit different aggregation tendencies.
View Article and Find Full Text PDFThe first fluorescent material for the referenced simultaneous RGB (red green blue) imaging of barometric pressure (oxygen partial pressure) and temperature is presented. This sensitive coating consists of two platinum(II) complexes as indicators and a reference dye, each of which is incorporated in appropriate polymer nanoparticles. These particles are dispersed in a polyurethane hydrogel and spread onto a solid support.
View Article and Find Full Text PDFThe synthesis and photophysical properties of a series of yellow-green to blue-green emitting heteroleptic, cyclometalated Pt(II)(acac) complexes based on substituted phenylpyridine and tetrahydroquinoline ligands is reported. The luminescence intensities and lifetimes of these compounds were also studied in poly(styrene) films with respect to their responses to oxygen and temperature. Particularly, due to the insensitivity to oxygen quenching, these complexes are promising candidates as inert reference dyes in optical sensors.
View Article and Find Full Text PDFThe structure-property correlations of a set of heteroleptic red- and green-emitting Ir(III) complexes with different temperature sensitivities and charge trapping capabilities are described, revealing superb performance in multi-layer phosphorescent organic light-emitting diodes (PhOLEDs) expressed by very high maximum luminous efficiencies up to 36.8 cd A(-1). Using 2-phenylpyridine and with 2-(naphthalen-1-yl)pyridine as the C^N ligand, the resulting red emitting complex featured a maximum luminous efficiency of 10.
View Article and Find Full Text PDFThe design, synthesis, photophysical and significantly improved electrooptical properties of a series of red emitting cyclometalated iridium(iii) complexes containing carbazolyl-acetylacetonate ligands are described.
View Article and Find Full Text PDFA new dual luminescent sensitive paint for barometric pressure and temperature (T) is presented. The green-emitting iridium(III) complex [Ir(ppy)(2)(carbac)] (ppy=2-phenylpyridine; carbac=1-(9H-carbazol-9-yl)-5,5-dimethylhexane-2,4-dione) was applied as a novel probe for T along with the red-emitting complex [Ir(btpy)(3)], (btpy=2-(benzo[b]thiophene-2-yl)pyridine) which functions as a barometric (in fact oxygen-sensitive) probe. Both iridium complexes were dissolved in different polymer materials to achieve optimal responses.
View Article and Find Full Text PDFThe efficient synthesis of novel beta-diketonates equipped with functional carbazolyl moieties and their subsequent transformations in 5-hexyl-thienyl substituted carbazole derivatives is presented by utilizing an effective Stille cross-coupling reaction. The introduced beta-diketonates served as ancillary ligands for novel heteroleptic red- and green-emitting Ir(III) complexes, when combined with 2-(naphthalen-1-yl)pyridine and 2-phenylpyridine as cyclometalating ligands. These novel Ir(III) complexes revealed color-tunability and a very good thermal stability until at least 207 degrees C.
View Article and Find Full Text PDFThe dimensionality of conjugated polymer systems plays an important role in energy-transfer processes, and 1D and 2D energy transfer of excitations are typically much slower than that between pi-stacked chains within a 3D polymeric solid. However, whether 2D energy transfer in conjugated polymers occurs mainly along polymer chains (intrachain), or between in-plain-adjacent polymer chains (interchain), has yet to be determined due to the difficulty of experimentally decoupling inter- and intrachain interaction in a 2D polymer system. This can be achieved by incorporating conjugated polymer chains into the planar galleries of layered matrices which sterically hinder polymer aggregation and pi-pi interchain interactions.
View Article and Find Full Text PDFThe need for novel materials with luminescent properties and advanced processing features requires reliable and reproducible synthetic routes for the design of suitable materials, such as e.g. polypyridyl ruthenium(II) and iridium(III)-containing polymers.
View Article and Find Full Text PDFA novel compound containing both a 2,2'-bipyridine as well as a 2-ureido-4[1H]-ureidopyrimidinone supramolecular moiety (3) has been synthesised and fully characterized by 1H-NMR, MALDI-TOFMS, UV-vis and IR spectroscopy. Subsequent coordination to iridium and ruthenium polypyridyl precursors allowed the formation of iridium(III) and ruthenium(II) polypyridyl dimers (5 and 7) assembled via quadruple hydrogen-bonding as well as metal coordination interactions. The syntheses and complete characterization of these materials by means of two-dimensional NMR techniques (1H-1H COSY and 1H-1H DOSY) as well as IR and MALDI-TOFMS are described in detail.
View Article and Find Full Text PDFElectrokinetic chromatography was employed to separate the enantiomers of two novel functionalized ruthenium(II) complexes with different polypyridyl coordination spheres. The use of anionic carboxymethyl-beta-cyclodextrin as chiral mobile phase additive resulted in maximum efficiency and resolution for the enantiomer separation of both transition metal complexes. The syntheses of the [4-(3-hydroxypropyl)-4'-methyl-2,2'-bipyridine]-bis(2,2'-bipyridine)rethenium(II)-bis(tetrafluoroborate) and [4-(3-hydroxypropyl)-4'-methyl-2,2'-bipyridine]-bis(4,4'-dimethyl-2,2'-bypyridine)ruthenium(II)-bis(tetrafluoroborate) complexes and their complete characterization by means of two-dimensional (1)H and (13)C[(1)H] NMR techniques ((1)H-(1)H COSY and (1)H-(13)C HMQC) as well as elemental analyses and MALDI-TOFMS are described in detail.
View Article and Find Full Text PDFWe examined the emission spectral properties of [Ru(bpy)(3)](2+) in a thin film of polyvinyl alcohol coated on quartz slides or on metallic silver particles. The relative intensities were several fold higher on the surface containing silver particles, and the decay times were several fold smaller. These results are consistent with an approximate 20-fold increase in the radiative decay rate of [Ru(bpy)(3)](2+) when near metallic silver particles.
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