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Studies of the energy spectrum of α, ω- substituted polymethine chains. II. Polymethine chains with odd number of methine groups
Authors:Nikolay Tyutyulkov  Fritz Dietz  Jürgen Fabian  Achim Melhorn  Alia Tadjer
Affiliation:(1) Chair of Physical Chemistry "ldquo"Wilhelm Ostwald"rdquo", University of Leipzig, 701 Leipzig, DDR;(2) Section Chemistry, Technical University of Dresden, 8027 Dresden, DDR;(3) Institute of Organic Chemistry, Academy of Sciences, 1113 Sofia, Bulgaria;(4) Present address: Institute of Organic Chemistry, Academy of Sciences, 1113 Sofia, Bulgaria
Abstract:The analysis of the experimental data for the energy of the longest wavelength optical transitions Deltaepsivn,opt of substituted polymethines X
$$dddot ---$$
(CH)2n+1
$$dddot ---$$
X shows that in the asymptotic case (nrarrinfin) Deltaepsivinfin,opt does not tend to zero, as it follows from the empirically established correlations, but has a finite, non-zero value. It is shown that the energy gap of odd polymethines is the same as that of the even polymethines - the polyenes (DeltaEinfinsim2 eV). The substituents (X epsi N, O, B) are responsible for the appearance of levels in the gap. These, depending on the substituent character, are vacant (X equiv B) or occupied (X equiv N, O). The transition from or to such a level determines the longest wavelength optical transition energy of polymethines.
Keywords:Polymethines,   /content/g656510206076616/xxlarge945.gif"   alt="  agr"   align="  BASELINE"   BORDER="  0"  >,   /content/g656510206076616/xxlarge969.gif"   alt="  ohgr"   align="  BASELINE"   BORDER="  0"  >- substituted  Polymethines, energy spectrum of   /content/g656510206076616/xxlarge8764.gif"   alt="  sim"   align="  MIDDLE"   BORDER="  0"  >
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