Kagawa, Yasuyuki (1998) New tetracyanoquinodimethane chromophores, synthesis and physical properties. Doctoral thesis, Durham University.
Synthesis and physical characterizations of a novel class of zwitterionic organic chromophores were carried out. A series of tetracyanoquinodimethane (TCNQ) derivatives was prepared from reactions with primary and secondary amines. By modifications of the structure it was hoped to optimize their nonlinear properties. The newly synthesized organic chromophores were highly polar, zwitterionic and transparent at wavelengths above 600nm, which is a requirement for waveguide devices at 650nm. The molecular dipole moments were determined experimentally and theoretically. The experimental dipole moments and the theoretical dipole moments were found to be in agreement. The nonlinear optical properties of the new compounds were studied using the Kurtz powder technique. Large second harmonic generation was observed from 7-(2,6, dimethylmorpholino)-7-(4-methylpiperidine)- 8,8-dicyanoquinomethane (25 times urea) as a result of the noncentrosymmetric crystal lattice (P2(_1)2(_1)2(_1)). A large twist between the donor moieties and the benzene ring was found from the crystallographic data, and compared with a theoretical model using an ab initio calculation. Strong fluorescence was observed in the solid states and glass forming solvents at low temperatures. An increase of the quantum yields as a function of viscosity was observed due to the constraining effect of the environment. Variations in the quantum yields from chromophore doped polymeric matrices such as PMMA at room temperature and at low temperature are attributed to the different "free volume" of the polymeric matrices. Possible mechanisms for the emission process in either viscous or non-viscous media are proposed. Photodegradation in solution was observed for illumination by a white light source. In parallel studies photodegradation in PMMA films was observed both in air and under vacuum. A possible photodegradation mechanism via free radicals, compatible with these experimental observations is suggested.
|Item Type:||Thesis (Doctoral)|
|Award:||Doctor of Philosophy|
|Copyright:||Copyright of this thesis is held by the author|
|Deposited On:||13 Sep 2012 15:58|