Hypsochromic Shift (hypsochromic + shift)

Distribution by Scientific Domains

Selected Abstracts

Acid,base behavior of triazoleporphyrazines in proton-donating media

O. G. Khelevina
Abstract The acid,base properties of some peripheral substituted triazoleporphyrazines in proton-donating media with poor-donating character were experimentally studied. The substitution of one pyrrole moiety in the porphyrazine-like compounds by one triazole ring in the triazoleporphyrazines leads to an increase in the basicity. The protonation of the triazoleporphyrazines results in a hypsochromic shift of the Q-bands in the UV,visible spectra. A DFT study of some selected structural models of the unsubstituted triazoleporphyrazine shows that the protonation strongly influences on the molecular electron structure of this compound and that it occurs preferentially through the nitrogen atom located at position 4 of triazole ring. The protonation through the other basic centers (the triazoleporphyrazine is a multicenter conjugated base) leads to different protonated forms which differ notably in their aromatic character. Therefore, this compound could be considered an intramolecular switch of aromaticity. Copyright © 2004 John Wiley & Sons, Ltd. [source]

Lewis Acid Modulation in a Amido-functional Diarylethene and Its Hypsochromism Effect

Xue-Dong Liu
Abstract A photochromic diarylethene, 1,2-bis(2-methyl-5-(4- N,N -dimethylaminophenyl)thien-3-yl)perfluorocyclopentene in proton-donating media was studied. The ammonium salt came into being in the presence of acetic acid following localization of lone pair electrons of the amino group. The maximum absorption of the salt had a 36 nm hypsochromic shift, and its molar extinction coefficient increased to 3.494×104 L·mol,1·cm,1. The conjugational and delocalizational energy levels were calculated by Gaussian 98, and its hypsochromic shift mechanism was also discussed. [source]

Photochromism of dihydroindolizines part VII: multiaddressable photophysical properties of new photochromic dihydroindolizines bearing substituted benzo[i]phenanthridine as a fluorescing moiety,

Saleh Abdel-Mgeed Ahmed
Abstract Sixteen benzo[i]phenanthridine derivatives 8a-p were prepared via photocyclization of cis-trans substituted 4-styrylquinolines in low-to-moderate yields. The chemical structure of the photocyclized benzo[i]phenanthridine derivatives was unambiguously elucidated by means of both spectral and analytical tools. The photochromic (PC) dihydroindolizines (DHIs) 8a-p based on benzo[i]phenanthridines were prepared in 19,57% yields via nucleophilic addition of benzo[i]phenanthridines 4a-p to spirocyclopropenes 5. The 1D, 2D, NOESY NMR spectra, mass spectrometry, and elemental analysis were used for characterization of the chemical structures of the newly synthesized DHIs 8a-p. Developing and tuning of the photophysical properties of the synthesized compounds by substituents in the base part have been achieved. The absorption maxima (,max) and the half-lives (t1/2) of the colored zwitterionic forms 7a-p were detected in all cases by flash-photolysis measurements due to the fast 1,5-electrocyclization back to the DHI system. Irradiation of DHI 8a-p in'CH2Cl2 solution with polychromatic light leads to the formation of green to green,blue colored betaines 7a-p after cooling with liquid nitrogen. The kinetics of the fast bleaching process of betaines 7a-p to DHIs 8a-p, studied by flash photolysis as well as low temperature FT-UV/VIS, were found to take place in the millisecond range (432,2675,ms) in dichloromethane solution and fitted well a first-order thermal back reaction. The fluorescence spectra as well as the fluorescence quantum yield were studied. Noticeable bathochromic and hypsochromic shifts in the emission spectra by changing the substituents in the base part were monitored. Interestingly, the photo-fatigue resistance of some studied betaines 7a-p showed a higher t30 -value than the standard one (dicyanopyridazine DHI). Large solvatochromic effects on the absorption maxima (,max) as well as a substantial increase in the half-lives (t1/2) with solvent polarity of betaines 7a-p were also observed. The multiaddressable PC properties of DHIs 8a-p will help these compounds to find applications. Copyright © 2007 John Wiley & Sons, Ltd. [source]

Synthesis and characterization of cyclopentadithiophene-based low bandgap copolymers containing electron-deficient benzoselenadiazole derivatives for photovoltaic devices

In Hwan Jung
Abstract We have synthesized two cyclopentadithiophene (CDT)-based low bandgap copolymers, poly[(4,4-bis(2-ethyl-hexyl)-4H -cyclopenta[2,1- b:3,4- b,]dithiophene-2,6-diyl)- alt -(benzo[c][1,2,5]selenadiazole-4,7-diyl)] (PCBSe) and poly[(4,4-bis(2-ethyl-hexyl)-4H -cyclopenta[2,1- b:3,4- b,]dithiophene-2,6-diyl)- alt -(4,7-dithiophen-2-yl-benzo[c][1,2,5]selenadiazole-5,5,-diyl)] (PCT2BSe), for use in photovoltaic applications. Through the internal charge transfer interaction between the electron-donating CDT unit and the electron-accepting benzoselenadiazole, we realized exceedingly low bandgap polymers with bandgaps of 1.37,1.46 eV. The UV,vis absorption maxima of PCT2BSe were subjected to larger hypsochromic shifts than those of PCBSe, because of the distorted electron donor,acceptor (D,A) structures of the PCT2BSe backbone. These results were supported by the calculations of the D,A complex using the ab initio Hartree-Fock method with a split-valence 6-31G* basis set. However, PCT2BSe exhibited a better molar absorption coefficient in the visible region, which can lead to more efficient absorption of sunlight. As a result, PCT2BSe blended with [6,6]-phenyl-C61 -butyric acid methyl ester (PC61BM) exhibited a better photovoltaic performance than PCBSe because of the larger spectral overlap integral with respect to the solar spectrum. Furthermore, when the polymers were blended with PC71BM, PCT2BSe showed the best performance, with an open circuit voltage of 0.55 V, a short-circuit current of 6.63 mA/cm2, and a power conversion efficiency of 1.34% under air mass 1.5 global illumination conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1423,1432, 2010 [source]