Spectroscopy and electrochemistry of new 6,6′-disubstituted-4,4′-bipyrimidine molybdenum(0) and tungsten(0) tetracarbonyl complexes

2005 ◽  
Vol 83 (8) ◽  
pp. 1114-1119 ◽  
Author(s):  
Elena Ioachim ◽  
Garry S Hanan

A new family of tetracarbonyl molybdenum(0) and tungsten(0) complexes based on new 6,6′-disubstituted-4,4′-bipyrimidine ligands was synthesized and characterized. The visible region of the absorption spectrum of each complex is dominated by a metal-to-ligand charge transfer band significantly lower in energy than the corresponding transition in 2,2′-bipyridine tetracarbonyl metal complexes. The 6,6′-substituents create a larger π-electronic system in the substituted bipyrimidines and are consequently better π acceptors than even the parent 4,4′-bipyrimidine. The absorption bands are shifted bathochromically with a decrease in solvent polarity.Key words: molybdenum and tungsten, nitrogen ligands, tetracarbonyl metal complexes, absorption spectroscopy, electrochemistry.

1995 ◽  
Vol 50 (4) ◽  
pp. 551-557 ◽  
Author(s):  
Kenta Takahashi ◽  
Keisuke Umakoshi ◽  
Akihiro Kikuchi ◽  
Yoichi Sasaki ◽  
Masato Tominaga ◽  
...  

New trinuclear rhodium(III) complexes, [Rh3(μ3-O)(μ-CH3COO)6(L)3]+ (L = imidazole (Him), 1-methylimidazole (Meim), and 4-methylpyridine (Mepy)) have been prepared. The Him, Meim, and Mepy complexes show reversible one-electron oxidation waves at E1/2 = +1.12, +1.12, and +1.28 V vs Ag/AgCl, respectively, in acetonitrile. Electronic absorption spectra of the one electron oxidized species of these complexes and [Rh3(μ3-O)(μ-CH3COO)6(py)3]+ (py = pyridine) (E1/2 = +1.32 V ) were obtained by spectroelectrochemical techniques. While the Rh3(III,III,III) states show no strong visible absorption, the Rh3(III,III,IV ) species give a band at ca. 700 nm (ε = 3390-5540 mol dm-3 cm-1). [Ir3(μ3-O)(μ-CH3COO)6(py)3]+ with no strong absorption in the visible region, shows two reversible one-electron oxidation waves at +0.68 and +1.86 V in acetonitrile. The electronic absorption spectrum of the one-electron oxidized species (Ir3(III,III,IV )) also shows some absorption bands (688 nm (ε, 5119), 1093 (2325) and 1400 (ca. 1800)). It is suggested that the oxidation removes an electron from the fully occupied anti-bonding orbital based on metal-dπ-μ3-O-pπ interactions, the absorption bands of the (III,III,IV ) species being assigned to transitions to the anti-bonding orbital.


Infra-red absorption spectroscopy of muscle has already been carried out, using the Burch reflecting microscope (Barer, Cole & Thompson 1949: Barer, Thompson & Williams unpublished). There are considerable difficulties involved in this type of work. In the first place it is rather doubtful whether such measurements will ever be possible on living muscle owing to the presence of water, which possesses intense absorption bands in some of the most useful regions of the infra-red spectrum. It may be possible to overcome this difficulty to some extent by using heavy water which has a different absorption spectrum. It is in principle possible to obtain information similar to that given by infra-red spectroscopy, even in the presence of water, by means of Raman spectroscopy, but the technical difficulties involved, particularly fight scattering by colloids, would seem to preclude this method of attack so far as muscle is concerned. Our infra-red measurements have hitherto been confined to dried material. The results indicate that there is little prospect of working with whole muscles, as even single isolated striated fibres of the frog, rabbit and crab were usually too thick. However, it was possible to obtain good spectra in the chemically important region from 3 to 14/ µ on exceptionally thin single fibres or on artificially compressed fibres. An attempt was made to detect dichroism by means of polarized infra-red radiation, but to our surprise none was observed throughout the 3 to 14 µ range, even though the material used showed strong birefringence in the visible region. Hr Stocken and I have recently examined certain molecular models of muscle, in the fight of the work of Ambrose, Elliott & Temple (1949) on myosin, and it now appears possible that infra-red dichroism of muscle might be expected to manifest itself only under rather special conditions. We hope to put these theoretical deductions to experimental test. As regards measurements on muscle in the ultra-violet region, the position is much more promising. It is quite possible to determine the absorption spectrum of the A or I band in living single fibres. The entire spectrum from about 230 m µ in the ultra-violet to over 600 m µ , in the visible can be recorded simultaneously, using the reflecting microscope. This technique can also be used with polarized ultra-violet fight, in order to detect variation of dichroism in crystals at different wave-lengths (Barer, Jope & Perutz unpublished), and I intend to apply it to the study of dichroism in muscle fibres. Another new possibility is the observation of birefringence, as well as dichroism, in the ultra-violet. I have recently carried out experiments with a view to developing a new type of ultra-violet polarizer and it should now be possible to use the reflecting microscope as an ultra-violet polarizing microscope.


2018 ◽  
Vol 15 (29) ◽  
pp. 164-170
Author(s):  
F. J. S. LIMA ◽  
L. H. M. da COSTA ◽  
A. O. da SILVA ◽  
F. C. PEREIRA

The purpose of this study was to analyze and quantify spectral parameters, the absorption bands, specifically in the uv-visible region of some N-oxide ligands. From the spectra, the area under the absorption band, the molar absorptivity, the integrated absorption coefficient and the oscillator strength by the Gaussian approximation method were calculated for each of them, using the proposed evaluation by Drago and Figgs. According to the obtained results, it can be concluded that the heterocyclic compounds studied absorb very well electromagnetic radiation in the ultraviolet region. For the ligands QUI-NO and NIC-NO it was observed that there are two types of bands, primary and secondary, being transitions of type π → π * and n → π*, respectively. For DITBIS-NO, there was only one primary band (transition 1) and two additional shoulders, which had the highest observed absorbance coefficient. These ligands are expected as potential electron donors in complex systems whose purpose is to change the energy levels of the electronic system in order to promote a better utilization of the absorbed energy and therefore a better efficiency.


1969 ◽  
Vol 47 (4) ◽  
pp. 637-645 ◽  
Author(s):  
J. F. Harrod

A series of phenoxo complexes of copper(II) containing a variety of halophenoxo ligands and a variety of amine ligands has been prepared. The thermal stability of the complexes with regard to the decomposition reaction:[Formula: see text]was found to be lower with those ligands, L, which increase the oxidizing power of the copper(II) and vice versa.The intense absorption bands in the visible region exhibited by these complexes have been assigned to a metal-to-ligand charge transfer process.


Molecules ◽  
2021 ◽  
Vol 26 (6) ◽  
pp. 1739
Author(s):  
Artyom A. Astafiev ◽  
Olga V. Repina ◽  
Boris S. Tupertsev ◽  
Alexey A. Nazarov ◽  
Maria R. Gonchar ◽  
...  

Arylazoimidazoles are important dyes which were intensively studied in the past. In contrast, triarylazoimidazoles (derivatives which carry aryl substituents at the imidazole core) received almost no attention in the scientific literature. Here, we report a new family of simple and easily accessible triarylazoimidazole-group 12 metal complexes, which feature highly efficient photo-luminescence emission (Φ up to  0.44). Novel compounds exhibit bright red emission in solution, which could be excited with a visible light.


Many years ago it was suggested by Hartley* that the limit of the solar spectrum towards the ultra-violet was attributable to absorption by atmospheric ozone, which, as he showed, would give rise to a general absorption beginning at about the place where the solar spectrum ends. In a recent paper by Prof. A. Fowler and myself,† the evidence for this view was very much strengthened. For it was shown that just on the limits of extinction the solar spectrum shows a series of narrow absorption bands which are eventually merged in the general absorption, and these narrow bands are precisely reproduced in the absorption spectrum of ozone. For my own part, I do not feel any doubt that ozone in the atmosphere is the effective cause limiting the solar spectrum.


An electronic absorption spectrum, attributed to phenyl, has been observed in the visible region with origin at 18 908 cm -1 after flash photolysis of benzene and halogenobenzenes. Similar spectra of fluoro, chloro and bromo phenyl are observed after flash photolysis of disubstituted benzenes. The vibrational structure of the phenyl spectrum has been analysed in terms of two fundamental frequencies at 571 and 896 cm -1 which correspond to the e 2 g and a 1 g frequencies of the B 2 u state of benzene. The ground state of phenyl has a π 6 n electronic configuration and the observed transition is interpreted as 2 A 1 → 2 B 1 resulting from a π → n excitation.


2018 ◽  
Vol 382 ◽  
pp. 369-373
Author(s):  
Usana Mahanitipong ◽  
Preeyapat Prompan ◽  
Rukkiat Jitchati

The four thiocyanate free ruthenium(II) complexes; [Ru(N^N)2(C^N)]PF6were synthesized and characterized for dye sensitized solar cells (DSSCs). The results showed that the broad absorptions covered the visible region from metal to ligand charge transfer (MLCT) were obtained with the main peaks at 560, 490 and 400 nm. The materials were studied DSSC performance under standard AM 1.5. Compound PP1 showed the power conversion efficiency (PCE) at 3.10%, with a short-circuit photocurrent density (Jsc) of 7.99 mA cm-2, an open-circuit photovoltage (Voc) of 563 mV and a high fill factor (ff) of 0.690.


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