4,5-Substituted C

We report the synthesis of seven novel backbone functionalized N-phenyl-1,3-thiazol-2-ylidene platinum(ii) complexes and their photophysical properties. Electronically diverse N-phenyl-1,3-thiazol-2-thiones were prepared by a reaction of aniline with carbon disulfide and different α-haloketone compounds. Oxidative desulfuration and salt metathesis yielded the desired NHC-precursors with hexafluorophosphate counterions. In addition, a new route for the synthesis of N-phenyl-1,3-benzo[d]thiazole tetrafluoroborate via N-arylation using hypervalent iodine species is presented. All complexes were prepared from the corresponding NHC precursor in a one-pot process using silver(i)oxide, transmetalation to platinum and reaction with the ß-diketone acetylacetone under basic conditions. These complexes exhibit strong phosphorescence with quantum yields up to 72% in 2 wt% PMMA films with decay lifetimes of 8.8-12.3 µs. The influence of methyl- and phenyl-groups, and an ester-substituent at the 4- and/or 5-position of the 1,3-thiazole moiety, as well as the N-phenyl-1,3-benzo[d]thiazole-derived motif is discussed. The 4,5-unsubstituted-N-phenyl-1,3-thiazol-2-ylidene platinum(ii) acetylacetonato complex served as a reference in this study to evaluate the electronic effects originating from the backbone substitution. All complexes emit in a narrow range of the bluish-green spectrum of the visible light (510 ± 10 nm).

Ruthenium(II) Bipyridyl Complexes with Cyclometalated NHC Ligands.

We present the synthesis and characterization of novel cyclometalated ruthenium N-heterocyclic carbene (NHC) complexes of the general formula [Ru(C^C*)(bpy)2]PF6 (bpy = 2,2'-bipyridine), with the C^C* ligand being based on different 1-phenylimidazoles. They were synthesized in a one-pot procedure starting from the corresponding p-cymene NHC complexes [Ru(C^C*)(p-cymene)Cl]. Their structural, spectroscopic, and electrochemical properties were investigated by NMR, X-ray, UV/vis, and CV, as well as density functional theory methods. Because of the stronger electron-donating carbene ligands, these complexes represent a new class of bisheteroleptic dyes with improved photophysical and electrochemical properties.

Changing the Emission Properties of Phosphorescent C

Cyclometalated thiazol-2-ylidene platinum(II) complexes based on the N-phenyl-4,5-dimethyl-1,3-thiazol-2-ylidene N-heterocyclic carbene (NHC) ligand and seven different ß-diketonate ligands have been synthesised and investigated for their structural and photophysical properties. The complexes were synthesised in a one-pot procedure starting with the in situ formation of the corresponding silver(I) carbene and transmetalation to platinum, followed by the reaction with the respective ß-diketonate under basic conditions. All the compounds were fully characterised by standard techniques, including 195 Pt NMR spectroscopy. Three solid-state structures revealed quite different aggregation behaviour depending on the ß-diketonate architecture. The reported complexes showed strong phosphorescence at room temperature in amorphous poly(methyl methacrylate) films. The emission wavelengths (ca. 510 nm) were found to be independent of the ß-diketonate ligand, but the electronically diverse ß-diketonates strongly influence the observed quantum yields (QY) and decay lifetimes. The results of theoretical studies employing density functional theory (DFT) methods support the conclusion of a metal-to-ligand charge transfer (3 MLCT) as the main emission process, in accordance with the reported photophysical properties. Standard organic light-emitting diodes (OLEDs) prepared with unoptimised matrix materials using one of the complexes showed values of 12.3 % external quantum yield, 24.0 lm W-1 luminous efficacy and 37.8 cd A-1 current efficiency at 300 cd m-2 .

Binuclear C

Binuclear C^C* cyclometalated NHC platinum(II) compounds with bridging amidinate ligands were synthesized to evaluate their photophysical properties. Their three-dimensional structures were determined by a combination of 2D NMR experiments, mass spectrometry, DFT calculations, and solid-state structure analysis. The bridging amidinate ligands enforce short distances between the platinum centers of the two cyclometalated structures, which gives rise to extraordinary photophysical properties.

Unusual dimer formation of cyclometalated ruthenium NHC p-cymene complexes.

We present the synthesis and structural characterization of novel ruthenium complexes containing C^C* cyclometalated N-heterocyclic carbene ligands, η(6)-arene (p-cymene) ligands and one bridging chlorine ion. Complexes of the general formula [Ru(p-cymene)(C^C*)Cl] were prepared via a one-pot synthesis using in situ transmetalation from the correspondent silver NHC complexes. These complexes react with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBAr(F)4) to form dinuclear complexes of the general structure [Ru(p-cymene)(C^C*)-µ-Cl-(p-cymene)(C^C*)Ru](+)[BAr(F)4](-). Solid-state structures confirm that the pseudo-tetrahedral coordination around the metal center with the η(6)-ligand aligned perpendicularly to the C^C* ligand and the i-Pr group "atop" is retained in the bimetallic complexes.