2,2 -bipyridyl spectroscopy

Luminescence spectroscopy is one of the most sensitive techniques for identification of impurities in dyes. The most commonly observed impurities in to-bipyridyl complexes of the type [RuL2X2] are the homoleptic tris-bipyridyl species [RuL3]2+. Since the emission quantum yields of the [RuL3]2+ complexes are significantly higher than those of the [RuL2X2] complexes, one can identify the homoleptic impurities at a level of less than 1%. This does depend, however, on the relative quantum yields, and position of the emission spectral maxima, for the complexes and impurities involved. 

The anion coordination properties of receptors such as compound [93] (Fig. 51) are currently under investigation. This molecule contains both a redox-active ruthenium bipyridyl moiety and also a cobaltocenium unit. This type of host has already been shown by 1H nmr and fluorescence emission spectroscopy to exhibit remarkable selectivity for the chloride anion in preference to dihydrogenphosphate (Beer and Szemes, 1995). 

The photochemical and thermal stabilities of Ru complexes have been investigated in detail [8,153-156]. For example, it has been reported that the NCS ligand of the N3 dye, cri-Ru(II)(dcbpy)2(NCS)2 (dcbpy = 2,2 -bipyridyl-4,4 -dicarboxylic acid), is oxidized to produce a cyano group (—CN) under irradiation in methanol solution. It was measured by both ultraviolet-visible (UV-vis) absorption spectroscopy and nuclear magnetic resonance (NMR) [8,153]. In addition, the intensity of the infrared (IR) absorption peak attributed to the NCS ligand starts to decrease at 135°C, and decarboxylation of N3 dyes occurs at temperatures above 180°C [155]. Desorption of the dye from the 2 surface has been observed at temperatures above 200°C. 

The double proton transfer of [2,2 -Bipyridyl]-3,3 -diol is investigated by UV-visible pump-probe spectroscopy with 30 fs time resolution. We find characteristic wavepacket motions for both the concerted double proton transfer and the sequential proton transfer that occur in parallel. The coherent excitation of an optically inactive, antisymmetric bending vibration is observed demonstrating that the reactive process itself and not only the optical excitation drives the vibrational motions. We show by the absence of a deuterium isotope effect that the ESIPT dynamics is entirely determined by the skeletal modes and that it should not be described by tunneling of the proton. 

Raman spectroscopy metal in water complexes, 309 Rare earth complexes acetylacetone synthesis, 377 guanidinium, 282 hydroxamic acids, 506 Redox properties bipyridyl metal complexes, 90 Reductive coupling nitrile metal complexes, 265 Resorcinol, 2,4-dinitro-metal complexes, 273 Rhenium complexes acetylacetone, 376 synthesis, 375, 378... 

The rates of hydrolysis of the trifhioroacetates (201 X = H, Me) increase in a nonlinear fashion in the presence of jS-CD. Some differences in rate between the two substrates have been explained as being due to different modes of inclusion.173 The novel CDs (202) and (203) have been synthesized in 45% and 66% yields, respectively, and their complexation with various l/d amino acids have been examined. Importantly, (202) and (203) can be detected by fluorescence spectroscopy and they can recognize the size and shape but also the chirality of the amino acids.174 A /j-CD dimer with a linking bipyridyl group (204) has been synthesized and shown to bind both ends of potential substrates into two different cavities of the CD holding the substrate ester carbonyl group directly above a Cu(H) ion bound to die bipyridyl unit. This achieves... 

Additional work by the Forster group, making use of transient emission spectroscopy, probed the rate of photoinduced electron transfer between metal centers within a novel trimeric complex [Os(II)(bpy)2(bpe)2 ] [Os(II) (bpy)2Cl]2 4+, where bpy is 2,2/-bipyridyl and bpe is fra s-l,2-bis-(4-pyridyl) ethylene. Transient emission experiments on the trimer, and on [Os(bpy)2(bpe)2]2+ in which the [Os(bpy)2Cl]+ quenching moieties are absent, reveal that the rate of photoinduced electron transfer (PET) across the bpe bridge is 1.3 0.1 x 108s-1. The electron transfer is believed to be from the peripheral Os(II)Cl metal centers to the [Os(bpy)2(bpe)2]2+ chro-mophore. Comparison to rate constants for reduction of monolayers at a Pt electrode reveals that the photoinduced process is significantly faster [39]. 

Layers of 4,4 -bipyridyl (0.3 mol T1 in dichloromethane) and ethyl bromoacetate (0.3 mol 1 1 in dichloromethane) and a separation layer of dichloromethane are fitted into each other by means of the concentric separation mixer [53]. The reaction temperature is 22 °C. The reaction solution is inserted as droplets or a continuous stream either directly or via the tubular reactor in the beaker. The precipitate solution yielded is passed through a frit and the remaining solid is washed with dichloromethane and dried at elevated temperature and weighed. The quatemized product is characterized by NMR spectroscopy. 

In 1963, Beattie and McQuillan (8) studied the IR spectra of MeSnCl3 complexes with pyridine, bipyridyl, and o-phenanthroline, the compositions being 1 2, 1 1, and 1 1, respectively. They obtained a rather complicated pattern of Sn—Cl vibrations and could make no structural assignment. Later it was shown (31, 81, 32) that IR spectroscopy is hardly applicable to the study of complexes of this type. In 1967, Wardell (151) studied the UV spectra of diethyl ether solutions of MeSnClj complexes with nitro-anilines and measured the equilibrium constants. The data were interpreted in terms of 1 1 complexes containing a five-coordinate tin (with 2,5- or 2,4-diaminonitrobenzenc) or a six-coordinate tin (with 3,4-di-aminonitrobenzene). 

In the first step, the precursor, typically a ruthenium or osmium bis(2,2,-bipyridyl) (bpy) complex, reacts with solvent (S) to produce a solvated complex. When solvents such as dry methanol and ethanol are used, only one chloride is exchanged and the species [Ru(bpy)2(PVP) Cl]+ is obtained as the sole product. The nature of the coordination sphere around the metal center can be determined by UV-visible (UV/Vis) spectroscopy (Xmax, 496 nm) and by its redox potential, (about 0.65 V (vs. SCE), depending on the electrolyte being used). By a systematic variation of the ratio of monomer units to redox-active centers, the loading of the polymer backbone ( n) can be varied systematically. (Here, n stands for the number of monomer units in the polymer per redox-active center, e.g. in a PVP-based, n = 10 polymer, there are 10 pyridine units for every redox center. 

Contzen J, Kostka S, Kraft R, Jung C. Intermolecular electron transfer in cytochrome P450cam covalently bound with tris(2,2 -bipyridyl)ruthenium(II) structural changes detected by FTIR spectroscopy. J Inorg Biochem 2002 91 607-17. 

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