Polymeric effects in optical-spectra of intermolecular charge-transfer complexesстатья
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Дата последнего поиска статьи во внешних источниках: 26 декабря 2017 г.
Аннотация:The charge transfer complexes between the donor diphenylbenzylamine (DPBA), and acceptors, hexabromodimethyl sulphone ((CBr3)2SO2) or CBr4, exhibit optical spectrum broadening when the liquid solution is substituted by a polymer matrix and narrowing as the temperature of the polymer composition increases. These effects may be explained by the dispersion of the DPBA twist angle phi (the angle between the phenyl ring plane and orbital of lone pair of electrons (LPE) on the nitrogen atom) in the restricted free volume of the polymer. The free volume fluctuations are effectively frozen because of high values of the relaxation times. The narrowing of the optical spectrum with increasing temperature is caused by the increasing polymer free volume. The existence of the twist angle phi dispersion brings about the inhomogeneous donor ‘ionization potentials’ distribution in relation to the acceptor interacting with the LPE as well as with the pi orbital of the donor. These polymer effects are not observed for the ferrocene (Fc) containing complex Fc.CBr4 because the latter includes a highly symmetrical donor molecule. The optical spectrum parameters of this complex depend only on the dielectric properties of the medium.