scholarly journals Photoswitchable stable charge-distributed states in a new cobalt complex exhibiting photo-induced valence tautomerism

2015 ◽  
Vol 185 ◽  
pp. 347-359 ◽  
Author(s):  
Michael Slota ◽  
Marian Blankenhorn ◽  
Eric Heintze ◽  
Minh Vu ◽  
Ralph Hübner ◽  
...  
Keyword(s):  
Charge Distribution ◽  
Cobalt Complex ◽  
Mixed Valence ◽  
Magnetic Behavior ◽  
Inert Atmosphere ◽  
Molecular Structures ◽  
Paramagnetic Resonance ◽  
Valence Tautomerism ◽  
X Band ◽  
Huge Impact

We report the synthesis and magnetic and photomagnetic behaviour of a novel valence tautomeric cobalt complex, [Co(3,5-dbbq)2(μ-bpym)] (1) (3,5-dbbq = 3,5-di-tert-butyl-1,2-benzoquinone and μ-bpym = 2,2′-bipyrimidine). The synthesis is performed by reacting Co2(CO)8 and μ-bpym in the presence of the ligand 3,5-dbbq in a mixed solvent under inert atmosphere. The magnetic behavior clearly shows the presence of electron transfer from the catecholate ligand to the cobalt center, producing valence tautomers of [CoII(SQ)2] with a transition temperature (T1/2) of 215 K. Photomagnetic studies, performed via both SQUID magnetometry and X-band electron paramagnetic resonance, show the clear presence of photoinduced valence tautomerism, at temperatures considerably higher than previous systems. A metastable charge distribution is observed, strengthening previous investigations on the character of mixed valence ligands. Entropy-driven valence tautomeric interconversion is observed, and drives the transition to the most stable charge distribution. The complex has the ability to coordinate and can be used as a photoswitchable building block, with the photomagnetic characterisation evidencing a metastable state lifetime of the photo-induced valence tautomeric process of ca. 2.9 × 104 s below 20 K. The observed yields are higher than ones in similar systems, showing that tiny changes in the molecular structures may have a huge impact.

scholarly journals Resolved Hyperfine at L-band for High-Spin CoEDTA, A Model for Co Sites in Proteins

2019 ◽  
Vol 20 (10) ◽  
pp. 2385
Author(s):  
William E. Antholine
Keyword(s):  
Accurate Determination ◽  
Cobalt Complex ◽  
Low Frequency ◽  
Paramagnetic Resonance ◽  
X Band ◽  
Epr Parameters ◽  
L Band ◽  
Band Spectra

Low-frequency electron paramagnetic resonance (EPR) spectra were obtained for the Co complex of ethylene diamine tetraacetic acid (CoEDTA). It was found that the cobalt hyperfine at geff-mid is better resolved at a low frequency, L-band (1.37 GHz), and not resolved at X-band (9.631 GHz), which is the conventional frequency used for most spectra for metal complexes. Resolved cobalt hyperfine lines lead to additional EPR parameters like A-mid for cobalt and a more-accurate determination of g-mid. Resolved hyperfine lines in the L-band, but not the S-band, spectra were obtained at a concentration of 1 mM. Knowing these additional EPR parameters provides a means to better determine the electron density in the ground state orbital for each cobalt complex, as well as to determine differences upon a change of ligation. If zinc sites can be replaced by cobalt, the cobalt spectra for these sites will enhance the characterization of the zinc sites.

scholarly journals Photoreactivity of Hair Melanin from Different Skin Phototypes—Contribution of Melanin Subunits to the Pigments Photoreactive Properties

2021 ◽  
Vol 22 (9) ◽  
pp. 4465
Author(s):  
Krystian Mokrzynski ◽  
Shosuke Ito ◽  
Kazumasa Wakamatsu ◽  
Theodore G. Camenish ◽  
Tadeusz Sarna ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Singlet Oxygen ◽  
Near Infrared ◽  
Paramagnetic Resonance ◽  
Time Resolved ◽  
W Band ◽  
Epr Oximetry ◽  
X Band ◽  
Hair Samples ◽  
Electron Paramagnetic

Photoreactivity of melanin has become a major focus of research due to the postulated involvement of the pigment in UVA-induced melanoma. However, most of the hitherto studies were carried out using synthetic melanin models. Thus, photoreactivity of natural melanins is yet to be systematically analyzed. Here, we examined the photoreactive properties of natural melanins isolated from hair samples obtained from donors of different skin phototypes (I, II, III, and V). X-band and W-band electron paramagnetic resonance (EPR) spectroscopy was used to examine the paramagnetic properties of the pigments. Alkaline hydrogen peroxide degradation and hydroiodic acid hydrolysis were used to determine the chemical composition of the melanins. EPR oximetry and spin trapping were used to examine the oxygen photoconsumption and photo-induced formation of superoxide anion, and time-resolved near infrared phosphorescence was employed to determine the singlet oxygen photogeneration by the melanins. The efficiency of superoxide and singlet oxygen photogeneration was related to the chemical composition of the studied melanins. Melanins from blond and chestnut hair (phototypes II and III) exhibited highest photoreactivity of all examined pigments. Moreover, melanins of these phototypes showed highest quantum efficiency of singlet oxygen photogeneration at 332 nm and 365 nm supporting the postulate of the pigment contribution in UVA-induced melanoma.

An X-band time domain electron paramagnetic resonance spectrometer

Pramana ◽  
1986 ◽  
Vol 27 (5) ◽  
pp. 661-677 ◽  
Author(s):  
Ranjan Das ◽  
Balu Venkataraman ◽  
Vinod R Bhagat ◽  
Ajit S Ghangrekar ◽  
Thomas Kuruvilla ◽  
...  
Keyword(s):  
Electron Paramagnetic Resonance ◽  
Time Domain ◽  
Electron Paramagnetic Resonance Spectrometer ◽  
Paramagnetic Resonance ◽  
X Band ◽  
Electron Paramagnetic

X-band electron paramagnetic resonance of a quasi-bidimensional molecular composite [NH3(CH2)4NH3]CuCl4

1996 ◽  
Vol 97 (8) ◽  
pp. 669-674 ◽  
Author(s):  
Jean-Claude Bissey ◽  
René Berger ◽  
Pierre Béziade ◽  
Nguyen-Ba Chanh ◽  
Thierry Maris ◽  
...  
Keyword(s):  
Electron Paramagnetic Resonance ◽  
Paramagnetic Resonance ◽  
Band Electron ◽  
X Band ◽  
Electron Paramagnetic

scholarly journals Tetramer Compound of Manganese Ions with Mixed Valence [MnII MnIII MnIV] and Its Spatial, Electronic, Magnetic, and Theoretical Studies

Crystals ◽  
2018 ◽  
Vol 8 (12) ◽  
pp. 447 ◽  
Author(s):  
Cándida Pastor-Ramírez ◽  
Rafael Ulloa ◽  
Daniel Ramírez-Rosales ◽  
Hugo Vázquez-Lima ◽  
Samuel Hernández-Anzaldo ◽  
...  
Keyword(s):  
Mixed Valence ◽  
Magnetic Behavior ◽  
Local Geometry ◽  
Spectroscopic Techniques ◽  
Theoretical Studies ◽  
The Novel ◽  
Manganese Ions ◽  
Computational Calculations ◽  
Valence Electrons ◽  
Coordination Reaction

Using different spectroscopic techniques and computational calculations, we describe the structural and electromagnetic relationship that causes many interesting phenomena within a novel coordination compound with mixed valence manganese (II, III and IV) in its crystal and powder state. The novel compound [MnII MnIII MnIV(HL)2(H2L)2(H2O)4](NO3)2(H2O) 1 was obtained with the Schiff base (E)-2-((2-hydroxybenzylidene)amine)-2-(hydroximethyl)propane-1,3-diol, (H4L), and Mn(NO3)2.4H2O. The coordination reaction was promoted by the deprotonation of the ligand by the soft base triethylamine. The paper’s main contribution is the integration of the experimental and computational studies to explain the interesting magnetic behavior that the mixed valence manganese multimetallic core shows. The results presented herein, which are rarely found for Mn(II), (III) and (IV) complexes, will contribute to the understanding of the magnetic communication generated by the valence electrons and its repercussion in the local geometry and in the overall crystalline structure.

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