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Charge Transfer Band (charge + transfer_band)
Selected AbstractsStudy of spectral properties of bis(1,10-phenanthroline) silicon hexacoordinated complexes by density functional theoryINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 14 2008Irina Irgibaeva Abstract Applying ab initio method the structures and UV-vis spectra of silicon hexacoordinated compound [Si(phen)2(OMe)2]I2 and it's nitrate [Si(phen)2(OMe)2](NO3)2 were calculated. On the ground of comparison of theoretical and experimental data (1H NMR and electronic absorption spectra) it was shown that the theoretical method B3LYP/LanL2DZ we have used describes bis(1,10-phenanthroline) silicon complexes reasonably well. On the basis of TDDFT calculations at B3LYP/LanL2DZ level it is predicted that [Si(phen)2(OMe)2]I2 compound has charge transfer band in UV-vis spectrum at 557 nm which is associated with electron transfer from I, to phen ligand while [Si(phen)2(OMe)2](NO3)2 doesn't have one. The absence of this band in the observed spectrum of the [Si(phen)2(OMe)2]I2 complex methanol solution (10,5 M) is explained by the dissociation of the complex into ions [Si(phen)2(OMe)2]2+ and 2I,. We assume that this charge transfer band corresponds to peak at 400 nm in UV-vis spectrum of [Si(phen)2(OMe)2]I2 thin film. The missing of such bands in UV-vis spectrum of nitrate [Si(phen)2(OMe)2](NO3)2 film is explained by n , p* nature of these transitions. Significant error in prediction of charge transfer band energy is due to failure of TDDFT method to yield underestimated charge transfer electronic energies. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Intramolecular electronic communication in a dimethylaminoazobenzene,fullerene C60 dyad: An experimental and TD-DFT studyJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2010K. Senthil Kumar Abstract An electronically push,pull type dimethylaminoazobenzene,fullerene C60 hybrid was designed and synthesized by tailoring N,N -dimethylaniline as an electron donating auxochrome that intensified charge density on the ,-azonitrogen, and on N -methylfulleropyrrolidine (NMFP) as an electron acceptor at the 4 and 4, positions of the azobenzene moiety, respectively. The absorption and charge transfer behavior of the hybrid donor-bridge-acceptor dyad were studied experimentally and by performing TD-DFT calculations. The TD-DFT predicted charge transfer interactions of the dyad ranging from 747 to 601 nm were experimentally observed in the UV-vis spectra at 721 nm in toluene and dichloromethane. A 149 mV anodic shift in the first reduction potential of the NN group of the dyad in comparison with the model aminoazobenzene derivative further supported the phenomenon. Analysis of the charge transfer band through the orbital picture revealed charge displacement from the n(NN) (nonbonding) and , (NN) type orbitals centered on the donor part to the purely fullerene centered LUMOs and LUMO+n orbitals, delocalized over the entire molecule. The imposed electronic perturbations on the aminoazobenzene moiety upon coupling it with C60 were analyzed by comparing the TD-DFT predicted and experimentally observed electronic transition energies of the dyad with the model compounds, NMFP and (E)-N,N -dimethyl-4-(p-tolyldiazenyl)aniline (AZNME). The n(NN) , ,*(NN) and ,(NN) , ,*(NN) transitions of the dyad were bathochromically shifted with a significant charge transfer character. The shifting of ,(NN) , ,*(NN) excitation energy closer to the n , ,*(NN) in comparison with the model aminoazobenzene emphasized the predominant existence of charge separated quinonoid-like ground state electronic structure. Increasing solvent polarity introduced hyperchromic effect in the ,(NN) , ,*(NN) electronic transition at the expense of transitions involved with benzenic states, and the extent of intensity borrowing was quantified adopting the Gaussian deconvolution method. On a comparative scale, the predicted excitation energies were in reasonable agreement with the observed values, demonstrating the efficiency of TD-DFT in predicting the localized and the charge transfer nature of transitions involved with large electronically asymmetric molecules with HOMO and LUMO centered on different parts of the molecular framework. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 [source] 3H -1,2-Dithiole-3-thione derivatives as novel solvatochromic dyesJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 11 2008Alejandro M. Fracaroli Abstract The UV,Vis spectrum of 5-(1-butylthio)-3H -1,2-dithiole-3-thione (1a) and that of the chromium pentacarbonyl complex of 5-methyl-3H -1,2-dithiole-3-thione (3) present significant changes with the solvent polarity. The two absorption bands shown by the compounds in the region above 300,nm were identified by theoretical calculations. For Compound 1a these are n,,* and ,,* transitions and for Compound 3 the longest wavelength absorption corresponds to a charge transfer band and shows a remarkably negative solvatochromism. Not only has the wavelength of maximum absorption changed with the solvent but also the ratio of the absorbances at the two wavelengths. The effect of solvents was correlated with solvatochromic parameters such as ,* and ,. The spectrum of 5-(1-butylthio)-3H -1,2-dithiole-3-one (2) was also measured in different solvents but in this case the changes observed are less significant than for the other two compounds. The spectra of 1a and 3 were also determined in the presence of anionic (SDS), cationic (CTAB), and neutral surfactants (Brig-35) and it is shown that these compounds can be used as probes for the polarity of the binding sites of organized assemblies. Copyright © 2008 John Wiley & Sons, Ltd. [source] Studies on Properties of p -Nitrophenylazo Calix[4]arene DerivativesCHINESE JOURNAL OF CHEMISTRY, Issue 2 2003Jin Chuan-Ming Abstract The p -nitrophenylazo calix[4]arene derivatives 1a-1d with nonlinear optical (NLO) properties were prepared by the diazo-coupling reaction of calix[4]arene with p -nitrophenyl diazonium. The diazotization reaction of p -nitroaniline was carried out with isoamyl nitrite as a source of nitrous add in EtONa/EtOH under refluxing condition. X-Ray crystallographic analysis and 1H NMR spectra reveal that they exist as cone conformation in crystal state or in solution. HRS measurements at 1064 nm in THF indicate that p -nitro-phenylazo calix[4]arenes have higher hyperpolarizability ,z values than the corresponding reference compound 4-(4-nitrophenylazo)-2, 6-dimethyl-phenol, without red shift of the charge transfer band. The tetrakis p -nitrophenylazo calix[4]arene (2) with longer alkyl chains can form monolayer at the air/water interface. [source] | ||||||||||