We report a new family of homoleptic iridium(III) complexes that emit blue phosphorescence at room temperature. The iridium(III) complexes are comprised of phenyltriazole ligands and were easily prepared via short synthetic routes. The parent fac-tris(1-methyl-5-phenyl-3-propyl-[1,2,4]triazolyl)iridium(III) complex exhibits blue photoluminescence (PL) with emission peaks at 449 and 479 nm and has a solution PL quantum yield of 66%. The emission was sequentially blue-shifted by the attachment of one and two fluorine atoms to the ligand phenyl ring with the fac-tris{1-methyl-5-(4,6-difluorophenyl)-3-propyl-[1,2,4]triazolyl}iridium(III) complex having the 1931 Commission Internationale de l'Eclairage coordinates of (0.16, 0.12) at room temperature. In contrast, when the phenyl ring of the ligands was substituted by trifluoromethyl, the PL spectrum was red-shifted when compared to the parent compound whereas if the trifluoromethyl group was attached to the triazole ring, the emission was blue-shifted. The radiative rates of these new blue iridium(III) complexes were found to be in the range of 2−6 × 105 s-1, indicating that the emission had varying amounts of metal-to-ligand charge-transfer character. Molecular orbital calculations showed that for the fluorinated complexes the contribution of the ligand triplet character to the emissive energy state increased with the hypsochromic shift in emission. This was confirmed by time-resolved PL measurements, which showed that the complex with the deepest blue emission had the slowest radiative decay rate.

The imidazo[1,5-a]pyridine skeleton provides a versatile platform for the generation of new types of stable N-heterocyclic carbenes. Rh(I) mono- (6) and biscarbenes (7) from imidazo[1,5-a]pyridin-3-ylidenes (ImPy) and derivatives such as 13 from a mesoionic carbene were synthesized and characterized.

The electrochemical reduction of Cu(II) bis(thiosemicarbazone) complexes [Cu(II)(btsc)] is accompanied by protonation to give an unstable Cu(I) intermediate [Cu(btscH(2))](+). The nature of this intermediate was probed by reaction of bis(thiosemicarbazone) ligands with a Cu(I) precursor which gave a novel helical dimeric dicationic complex. The dependence of these reactions on the ligand backbone substituents is discussed together with their possible relevance to the use of Cu(II) bis(thiosemicarbazone) ligands as hypoxic selective imaging and therapeutic agents.

Two new types of unsymmetrical bis(thiosemicarbazone) proligands and their neutral zinc(II) and copper(II) complexes have been synthesized. These bifunctional ligands both chelate the metal ions and provide pendent amino groups that can be readily functionalized with biologically active molecules. Functionalization has been demonstrated by the synthesis of three water-soluble glucose conjugates of the new zinc(II) bis(thiosemicarbazonato) complexes, and their copper(II) analogues have been prepared in aqueous solution via transmetalation. A range of techniques including NMR, electron paramagnetic resonance, cyclic voltammetry, high-performance liquid chromatography (HPLC), UV/vis, and fluorescence emission spectroscopy have been used to characterize the complexes. Four compounds, including two zinc(II) complexes, have been characterized by X-ray crystallography. The connectivity and conformation of the glucose conjugates have been assigned by NMR spectroscopy. Time-dependent density functional theory calculations have been used to assign the electronic transitions of the copper(II) bis(thiosemicarbazonato) chromophore. Two copper-64-radiolabeled complexes, including one glucose conjugate, have been prepared and characterized using radio-HPLC, and transmetalation is shown to be a viable method for radiolabeling compounds with copper radionuclides. Preliminary cell washout studies have been performed under normoxic conditions, and the uptake and intracellular distribution have been studied using confocal fluorescence microscopy.

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The uptake of zinc bis(thiosemicarbazone) complexes in human cancer cells has been studied by fluorescence microscopy and the cellular distribution established, including the degree of uptake in the nucleus.

[structure: see text] A vinylene-linked porphyrin dimer, with no substituents at the beta-positions, has been synthesized by CuI/CsF promoted Stille coupling. In the crystal structure of this dimer, the C(2)H(2) bridge is twisted by 45 degrees relative to the plane of the porphyrins. The absorption, emission spectra, and electrochemistry reveal substantial porphyrin-porphyrin pi-conjugation. The triplet excited-state absorption spectrum of this dimer makes it suitable for reverse saturable absorption at 710-900 nm.

A wide range of pseudorotaxane assemblies containing positively charged pyridinium, pyridinium nicotinamide, imidazolium, benzimidazolium and guanidinium threading components, and macrocyclic isophthalamide polyether ligands have been prepared using a general anion templation procedure. In noncompetitive solvent media, coupling halide anion recognition by a macrocyclic ligand with ion-pairing between the halide anion and a strongly associated cation provides the driving force for interpenetration. Extensive solution 1H NMR binding studies, thermodynamic investigations, and single-crystal X-ray structure determinations reveal that the nature of the halide anion template, strength of the ion-pairing between the anion template and the cationic threading component, and to a lesser extent favorable second sphere pi-pi aromatic stacking interactions between the positively charged threading component and macrocyclic ligand, together with macrocyclic ring size, affect the efficacy of pseudorotaxane formation.