2013

5.
A Donor–Acceptor Tetrathiafulvalene Ligand Complexed to Iron(II): Synthesis, Electrochemistry, and Spectroscopy of [Fe(phen)2(TTF-dppz)](PF6)2
N. Dupont, Y.-F. Ran, S.-X. Liu, J. Grilj, , S. Decurtins and
Inorganic Chemistry, in press , 2013
DOI:10.1021/ic3019277 | Abstract | Article HTML | Article PDF
 
The synthesis and photophysical properties of the complex [Fe(phen)2(TTF-dppz)]2+ (TTF-dppz = 4′,5′-bis-(propylthio)tetrathiafulvenyl[i]dipyrido[3,2-a:2′,3′-c]phenazine, phen = 1,10-phenanthroline) are described. In this complex, excitation into the metal–ligand charge transfer bands results in the population of a high-spin state of iron(II), with a decay lifetime of approximately 1.5 ns, in dichloromethane, at room temperature. An intraligand charge transfer state can also be obtained and has a lifetime of 38 ps. A mechanism for the different states reached is proposed based on transient absorption spectroscopy.
  
4.
Excited-state dynamics of porphyrin-naphthalenediimide-porphyrin triads
, S. Bhosale, S.J. Langford and
Physical Chemistry Chemical Physics, 15 (4) , 2013, p1177-1187
DOI:10.1039/c2cp43595k | Abstract | Article PDF
The excited-state dynamics of two triads consisting of a naphthalenediimide (cNDI) substituted at the core by two zinc (ZnP) or free-base tetraphenylporphyrins (FbP) was investigated by ultrafast fluorescence and transient absorption spectroscopy. The electronic absorption spectra of the triads are almost the composites of those of the constituents, pointing to a weak electronic coupling and to a localization of the excitation energy on one of the porphyrins. In cyclohexane, the excited-state dynamics of the triads are essentially the same as those of the individual porphyrins, with the exception of the Soret emission of the ZnP triad, whose lifetime exhibits a more than 10 fold shortening compared to ZnP. A similarly ultrafast fluorescence decay was measured in tetrahydrofuran and benzonitrile. In these two solvents, charge separation from the excited porphyrin to the cNDI was found to take place with ~1 ps and ~25 ps time constants in the ZnP and FbP triads, respectively. The build up of the charge-separated state population in the ZnP triad is independent on the excitation wavelength, indicating that charge separation takes place from the lowest singlet excited state. Charge recombination occurs with a time constant around 8 ps in both triads, i.e. is slower than charge separation in the ZnP triad but faster in the FbP triad. These differences are rationalized in terms of the driving forces for charge separation and recombination.
3.
First-Principles Simulation of Absorption Bands of Fluorenone in Zeolite L
, , G. Tabacchi, E. Fois, G. Calzaferri and A. Devaux
Physical Chemistry Chemical Physics, 15 (1) , 2013, p159-167
DOI:10.1039/c2cp42750h | unige:24518 | Abstract | Article PDF
 
The absorption spectrum of fluorenone in zeolite L is calculated from first-principles simulations. The broadening of each band is obtained from the explicit treatment of the interactions between the chromophore and its environment in the statistical ensemble. The comparison between the simulated and measured spectra reveals the main factors affecting the spectrum of the chromophore in hydrated zeolite L. Whereas each distinguishable band is found to originate from a single electronic transition, the bandwidth is determined by the statistical nature of the environment of the fluorenone molecule. The K+...O=C motif is retained in all conformations. Although the interactions between K+ and the fluorenone carbonyl group result in an average lengthening of the C=O bond and in a redshift of the lowest energy absorption band compared to gas phase or non-polar solvents, the magnitude of this shift is noticeably smaller than the total shift. An important factor affecting the shape of the band is fluorenone’s orientation, which is strongly affected by the presence of water. The effect of direct interactions between fluorenone and water is, however, negligible.
  
2.
Effect of Pressure on the Free Ion and Crystal Field Parameters of Sm2+ in BaFBr and SrFBr Hosts
P. Pal, T. Penhouët, and
Journal of Luminescence, 134 , 2013, p678-685
Keywords: Sm2+high pressure luminescencecrystal fieldBaFBrSrFBr
DOI:10.1016/j.jlumin.2012.07.010 | unige:24061 | Abstract | Article HTML | Article PDF
The emission spectra of Sm2+ doped in BaFBr and SrFBr hosts were measured at 10 K from ambient pressure to 8 GPa. The crystal field energy levels determined from the emission spectra were used to extract the free ion parameters (Fk and ζ ) and crystal field parameters (Bqk). The variation of Fk and ζ as a function of pressure was studied systematically and was discussed in relation to the central field and symmetry restricted covalency models. The change of the spin orbit coupling parameter (ζ) with pressure for SrFBr:Sm2+ showed very different behavior than in other matlockite hosts. Moreover the variation of Bqk under pressure was studied. The pressure dependence of the Bqk was described quantitatively using the Superposition Model (SM) with the help of structural parameters as a function of pressure, obtained from periodic DFT calculations. The validity of the SM was tested for Sm2+ in BaFBr and SrFBr. It is shown that this model does not apply to SrFBr, in contrast to other matlockite host materials.
1.
Chromium(III)-trisoxalate, a versatile building block for luminescent materials
M. Milos and
Journal of Luminescence, 133 , 2013, p15-20
Keywords: chromium(III)-tris-oxalateenergy migrationfluorescence line narrowingspectral diffusionpersistent spectral hole burning
DOI:10.1016/j.jlumin.2011.12.053 | unige:24060 | Article HTML | Article PDF
 
Chromium(III)-trisoxalate,[Cr(ox)3]3- (ox = C2O42-), incorporated into polymeric networks of composition [NaCr(ox)3][MII(bpy)3] and [NaCr(ox)3][MIII(bpy)3]ClO4 (bpy= 2,2'-bipyridine, MII = Zn, Fe, Ru; MIII = Rh, Cr), results in interesting features ranging from phonon-assisted and resonant energy migration within the R1 line the 2E state to persistent spectral side-hole burning via the latter, and manifestations of specific nearest-neighbour π–π interactions between bipyridine and oxalate.



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Dernière mise à jour le 02/1/2013