Search results for "Pyridine"
showing 10 items of 2516 documents
Excited State Tuning of Bis(tridentate) Ruthenium(II) Polypyridine Chromophores by Push-Pull Effects and Bite Angle Optimization: A Comprehensive Exp…
2013
The synergy of push-pull substitution and enlarged ligand bite angles has been used in functionalized heteroleptic bis(tridentate) polypyridine complexes of ruthenium(II) to shift the (1) MLCT absorption and the (3) MLCT emission to lower energy, enhance the emission quantum yield, and to prolong the (3) MLCT excited-state lifetime. In these complexes, that is, [Ru(ddpd)(EtOOC-tpy)][PF6 ]2 , [Ru(ddpd-NH2 )(EtOOC-tpy)][PF6 ]2 , [Ru(ddpd){(MeOOC)3 -tpy}][PF6 ]2 , and [Ru(ddpd-NH2 ){(EtOOC)3 -tpy}][PF6 ]2 the combination of the electron-accepting 2,2';6',2''-terpyridine (tpy) ligand equipped with one or three COOR substituents with the electron-donating N,N'-dimethyl-N,N'-dipyridin-2-ylpyridin…
Coordination of expanded terpyridine ligands to cobalt
2013
Abstract The tridentate expanded terpyridine-like ligand N,N′-dimethyl-N,N′-dipyridin-2-yl-pyridin-2,6-diamine (ddpd) and [Co(H2O)6](BF4)2 give the high-spin complex mer-[Co(ddpd)2](BF4)2 with a tetragonally compressed CoN6 coordination geometry according to X-ray diffraction and SQUID measurements. UV–Vis–NIR spectra indicate a large ligand field splitting close to the high-spin/low-spin crossover point. Oxidation of the CoII complex to CoIII is achieved with silver triflate. The self exchange between high-spin CoII and low-spin CoIII is slow on the NMR time scale.
Anionic Cyclometalated Iridium(III) Complexes with a Bis-Tetrazolate Ancillary Ligand for Light-Emitting Electrochemical Cells
2017
none 10 si A series of monoanionic Ir(III) complexes (2-4) of general formula [Ir(C^N)2(b-trz)](TBA) are presented, where C^N indicates three different cyclometallating ligands (Hppy = 2-phenylpyridine; Hdfppy = 2-(2,4-difluoro-phenyl)pyridine; Hpqu = 2-methyl-3-phenylquinoxaline), b-trz is a bis-tetrazolate anionic N^N chelator (H2b-trz = di(1H-tetrazol-5-yl)methane), and TBA = tetrabutylammonium. 2-4 are prepared in good yields by means of the reaction of the suitable b-trz bidentate ligand with the desired iridium(III) precursor. The chelating nature of the ancillary ligand, thanks to an optimized structure and geometry, improves the stability of the complexes, which have been fully char…
Nonheme Fe(IV) Oxo Complexes of Two New Pentadentate Ligands and Their Hydrogen-Atom and Oxygen-Atom Transfer Reactions.
2015
Two new pentadentate {N5} donor ligands based on the N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) framework have been synthesized, viz. [N-(1-methyl-2-benzimidazolyl)methyl-N-(2-pyridyl)methyl-N-(bis-2-pyridyl methyl)amine] (L1) and [N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L2), where one or two pyridyl arms of N4Py have been replaced by corresponding (N-methyl)benzimidazolyl-containing arms. The complexes [FeII(CH3CN)(L)]2+ (L = L1 (1); L2 (2)) were synthesized, and reaction of these ferrous complexes with iodosylbenzene led to the formation of the ferryl complexes [FeIV(O)(L)]2+ (L = L1 (3); L2 (4)), which were characterized by UV–vis spe…
A Heteroleptic Push-Pull Substituted Iron(II) Bis(tridentate) Complex with Low-Energy Charge-Transfer States
2014
A heteroleptic iron(II) complex [Fe(dcpp)(ddpd)](2+) with a strongly electron-withdrawing ligand (dcpp, 2,6-bis(2-carboxypyridyl)pyridine) and a strongly electron-donating tridentate tripyridine ligand (ddpd, N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine) is reported. Both ligands form six-membered chelate rings with the iron center, inducing a strong ligand field. This results in a high-energy, high-spin state ((5) T2 , (t2g )(4) (eg *)(2) ) and a low-spin ground state ((1) A1 , (t2g )(6) (eg *)(0) ). The intermediate triplet spin state ((3) T1 , (t2g )(5) (eg *)(1) ) is suggested to be between these states on the basis of the rapid dynamics after photoexcitation. The low-energy …
Structural chemistry of complexes of ( ? 1)d s metal ions with ?-N-donor substituted thiolate ligands (=0, 2)
2005
Abstract The molecular structures of several d 10 metal ion complexes with 2-amino or 2-imino substituted thiolate ligands, derived from 2-aminoethanethiol, 2-(mercaptomethyl)pyridine, 2-aminobenzenethiole, and 8-mercaptoquinoline, are presented. Since ligand field stabilization energy is absent, the complexes display a large variety of co-ordination numbers and geometries around the metal centers. Distortions from ideal tetrahedral or trigonal bipyramidal configurations are discussed in terms of special structural parameters. In contrast to thiolate ligands that lack additional donor atoms and thus form oligo- or poly-nuclear complexes, the β-N donor group stabilizes mono-nuclear complexes…
Synthesis and chemical characterization of CuII, NiII and ZnII complexes of 3,5-bis(2′-pyridyl)-1,2,4-oxadiazole and 3-(2′-pyridyl)5-(phenyl)-1,2,4-o…
2011
Abstract The synthesis and structural characterization of Ni II , Cu II and Zn II complexes of two chelating 1,2,4-oxadiazole ligands, namely 3,5-bis(2′-pyridyl)-1,2,4-oxadiazole (bipyOXA) and 3-(2′-pyridyl)5-(phenyl)-1,2,4-oxadiazole (pyOXA), is here reported. The formed hexacoordinated metal complexes are [M(bipyOXA) 2 (H 2 O) 2 ](ClO 4 ) 2 and [M(pyOXA) 2 (ClO 4 ) 2 ], respectively (M = Ni, Cu, Zn). X-ray crystallography, 1 H and 13 C NMR spectroscopy and C, N, H elemental analysis data concord in attributing them an octahedral coordination geometry. The two coordinated pyOXA ligands assume a trans coplanar disposition, while the two bipyOXA ligands are not. The latter result is a possib…
Excited-state lifetimes of [Fe (bipy)3]2+ and [Fe(phen)3]2+
1990
Abstract In the low-spin [Fe(bipy)3]2+ (bipy = 2,2′,bipyridine) and [Fe(phen)3]2+ (phen = 1,10-phenanthroline) complexes an excited high-spin 5T2 ligand field state can be populated by irradiating into the 1MLCT absorption band at 530 nm. The lifetimes of this excited state at low temperatures are reported for [Fe(bipy)3]2+ doped into [Zn(bipy)3] (PF6)2 and [Zn(bipy)3] (BF4)2 and for [Fe(phen)3]2+ and [Fe(bipy)3]2+ embedded in the ion exchange polymer Nafion. For [Fe(bipy)3]2+ in [Zn(bipy)3](PF6)2 the observed lifetimes decrease from 1600 ns at 10 K to 14 ns at 125 K.
Synthesis and characterization of new aromatic tweezers and complex formation with tropylium ion in 1,2-dichloroethane
2001
A series of benzene and pyridine tweezers bearing phenyl, naphthyl and anthryl receptor units was prepared and characterized. The x-ray crystal structure of the 1,3-bis(9-methanolanthracene)methylbenzene ligand (5) is reported. UV–visible and NMR spectroscopy were used to investigate the host–guest chemistry of the new ligands in complexation with tropylium tetrafluoroborate as a model aromatic cationic guest in 1,2-dichloroethane. The appearance of coloured charge-transfer absorption bands demonstrates the complex formation with a tropylium ion. The enlargement of aryl receptor size from phenyl and naphthyl to anthryl increases the stability of complexes. Electron donor–acceptor interactio…
Molecular Engineering of Iridium Blue Emitters Using Aryl N‐Heterocyclic Carbene Ligands
2016
The synthesis of a new series of neutral bis[2-(2,4-difluorophen-2-yl)pyridine][1-(2-aryl)-3-methylimidazol-2-ylidene]iridium(III) complexes is reported. Each complex has been characterized by NMR spectroscopy, UV/Vis spectrophotometry, and cyclic voltammetry, and the photophysical properties examined in depth. Furthermore, two of the complexes have been characterized by single-crystal X-ray diffraction analysis. By systematically modifying the cyclometalating aryl group on the N-heterocyclic carbene (NHC) ligand from 2,4-dimethoxyphenyl to 6-methoxy-2-methyl-3-pyridyl, the energy levels of the Ir complexes were modified to produce new blue emitters with increased HOMO and triplet-state ene…