1628644-36-9Relevant articles and documents
Photophysical Properties of Oligo(phenylene ethynylene) Iridium(III) Complexes Functionalized with Metal-Anchoring Groups
Ponce, Julia,Aragó, Juan,Vayá, Ignacio,Magenti, Jorge Gómez,Tatay, Sergio,Ortí, Enrique,Coronado, Eugenio
, p. 1851 - 1859 (2016)
The electrochemical and photophysical properties of a family of conjugated ligands and their iridium(III) cyclometallated complexes are described. They consist of a series of monocationic IrIII bis-2-phenylpyridine complexes with p-phenylethynyl-1,10-phenanthroline ligands of different length. The structure of these ligands includes terminal acetylthiol or pyridine groups, which can provide good electrical contacts between metal electrodes. Cyclic voltammetry, absorption and emission spectroscopy, laser flash photolysis and density functional theory calculations reveal that the high conjugation of the diimine ligand affords small energy gaps between the frontier orbitals. Nevertheless, the nature of the terminal substituents and the extent of the conjugation in the diimine ligand have little influence on the photophysical features at room temperature. The spectroscopic data and theoretical calculations agree that the charge-transfer nature of the emitting excited state is maintained along the series at room temperature, whereas in rigid matrices ligand-centred states also contribute to the low-temperature emission. The good conducting features of the diimine ligands, the small dependence of the HOMO-LUMO (HOMO = highest occupied molecular orbital, LUMO = lowest unoccupied molecular orbital) gaps of these complexes on the ligands and the charge-transfer nature of the emitting excited state make these complexes promising test beds for the study of photoconducting phenomena in molecular junctions.
Alternative preparation and characterization of platinum(II) organometallic dinuclear complexes and oligomers with 3,8-diethynylphenanthroline derivatives
Shiotsuka, Michito,Hashimoto, Takuto,Matsubara, Kenta,Sako, Katsuya
, p. 693 - 703 (2018/07/21)
Novel platinum(II) organometallic dinuclear complexes and oligomers with two types of phenanthroline ligands, namely 3,8-diethynylphenanthroline (L1) and 3,8-bis-(4-ethynyl-phenylethynyl)-1,10-phenanthroline (L2), were synthesized from trans-Pt(PBu3)2(1-ethynyl-4-methyl-benzene)Cl and trans-Pt(PBu3)2Cl2 by transmetalation of copper ion. The alternative procedure targeted platinum oligomer termination selection of either chloride or respective phenanthrolines and was successfully performed with different purifications by extraction and column chromatography. The structural formulae of these platinum complexes and oligomers were revealed with by analysis of both 31P{1H}-NMR and 1H-NMR spectral data. Alternative preparations of platinum oligomers with two types between chloride and respective phenanthroline termination are very useful for the selective synthesis for hybrid polymers with the coupling reaction with two different platinum oligomers with different diethynylaryl ligands. The platinum organometallic compounds showed similar absorption bands in the UV–Vis region. Those prepared with L1 had a strong absorption band at around 400?nm, assignable to the lowest energy metal-perturbed 1[π–π*] transitions, while in compounds prepared with L2, the strong band appeared around 410?nm, because L2 has an extended π conjugation relative to L1. No distinct differences were observed in the absorption spectra of these platinum oligomers between the different terminal structures, chloride or various phenanthrolines. The luminescence spectra of the platinum compounds prepared with either L1 or L2, however, showed a distinct difference. Those with L1 showed only a phosphorescence assignable to a typical metal-perturbed 3[π–π*] transition with vibronic progressions centered at around 530?nm in deoxygenated CH2Cl2 at room temperature, while those with L2 showed weak dual emissions assignable to a mixture of typical metal-perturbed 1[π–π*] and 3[π–π*] transitions in the visible region.
Fast pirouetting motion in a pyridine bisamine-containing copper-complexed rotaxane
Coronado, Eugenio,Gavina, Pablo,Ponce, Julia,Tatay, Sergio
, p. 6939 - 6950 (2014/06/09)
The present work reports the introduction of pyridine bisamine terdentate ligands in the structure of a pirouetting copper rotaxane. Rotaxane 2[PF 6] constitutes the first example of the incorporation of imine-based dynamic covalent chemistry in the synthesis of switchable copper-complexed interlocked systems. In this rotaxane, the substitution of the classical terpyridine terdentate unit by a pyridine bisamine moiety has led to a significant stabilization of the pentacoordinated site. That fact has been evidenced by EPR spectroscopy and cyclic voltammetry. Regarding the tetracoordinated site, the congestion around the coordination sphere has been reduced to accelerate the typically slow reorganization of the CuII. Ethynyl-3,8-substitution on the axis phenanthroline along with the 2,9-diphenyl-1,10-phenanthroline (dpp) present in the macrocycle afforded a very stable coordination environment for CuI, which is at the same time labile upon oxidation. In summary, the incorporation of a pyridine bisamine unit as a terdentate ligand and the optimization of the bidentate ligand of the axle not only has led to a simplification of the synthetic procedures, but it has also given rise to a bistable systems with an enhanced energetic separation between states and an acceleration of the reorganization processes. Thus far, rotaxane 2[PF6] presents the fastest switching cycle reported to date in copper-interlocked dynamic systems.
