Poly excitonic structure

The kinetics captured in disordered systems like polymers, glasses and poly-cristalline structures has been often described in terms of continuous relaxation times and exciton diffusion at recombination centers [10]. Assuming a <5— pulse function, the temporal data are best fitted by a monomolecular kinetic equation,... 

As well known, so-called excimer sites exist in poly-N-vinylcarbazole. It is well established that these excimer sites are the efficient traps for the singlet and triplet excitons, which migrate along the polymer chain. The structure of these sites are thought to be a special conformation having a pair of carbazolyl groups arranged parallel each other. 

The secondary structure of poly(iV-alkynylamides) is influenced by the position of the chiral center and amide group.The position of the chiral center mainly affects the helical pitch, which becomes short when the chiral center is positioned away from the main chain. The stability of the helical structure is also influenced by the position of the amide group. Based on molecular orbital study, it is concluded that poly(iV-propargylamides) with right-handed helical structure display a plus Cotton effect around 390 nm. This is also confirmed by the exciton chirality method using porphyrin as a chromophore. ... 

However, disorder appears to be crucial in the occurrence of photoexcited paramagnetic centers since irradiation of single crystal samples, e.g. poly TS, has no effect. The energy levels in the low energy absorption tail of the disordered samples play an important part. It is not clear if these derive from excitonic or interband transitions but it should be noted that in principle any distortion of the polymer chain can lead to defect states in the optical gap ( ) and that the weak absorption tail in crystals is a major factor determining photoconduction (9 ). Thus, it appears that a basis exists for the correlation of structure and the intrinsic absorption spectra but that further efforts are required to obtain a better understanding of defect states and their spectroscopic properties. 

Figure 4.46. Molecular structures of commonly used OLED/PLED materials. Shown are (a) Alq3 (tris(quinoxalinato)Al (III)) used as an electron-transport material (b) DIQA (diisoamylquinacridone) used as an emissive dopant (c) BCP (2,9-dimethyl-4,7-diphenyl-l,10-phenanthroline) used as an exciton/ hole blocking agent (d) NPB (l,4-bis(l-napthylphenyl amino)biphenyl) (e) PFO (9,9-dioctylfluorene) used as an emissive polymer in PLEDs (f) PEDOT-PSS (poly-3,4-ethylenedioxythiophene-polystyrene sulfonate) used as a hole transport material in PLEDs.

Poly(phenylene vinylene), PPV, and its soluble derivatives have emerged as the prototypical luminescent semiconducting polymers. Since PPV has a nondegenerate ground state, structural relaxation in the excited state leads to the formation of polarons, bipolarons, and neutral excitons. However, prior to treating the structural relaxation in the excited state, one needs to develop a satisfactory description of the electronic excited states. 

Huige and Hezemans179 180 have performed extensive molecular mechanics calculations using the consistent force-field method on various oligo- and polyisocyanides. The hexadecamer of ferf-butyl isocyanide was calculated to have a helical middle section and disordered ends. The dihedral angle N=C—C=N in the middle section was found to be 78.6°, and the number of repeat units per helical turn was 3.75. The latter number is in agreement with circular dichroism calculations using Tinoco s exciton theory (3.6—4.6) and De Voe s polarizability theory (3.81). The molecular mechanics calculations further predicted that the less bulky polymers 56 and 57 form helical polymers as well, whereas a disordered structure was calculated for poly(methyl isocyanide) (55). 

In order to proceed it is now necessary to consider the nature of the lowest excited state of these polymers. One description which appears to be particularly appropriate to these materials is that given by the molecular exciton theory (37,38). This of course is suggested by the nature of the fluorescence spectrum itself and in addition this approach has proven to be quite successful in the Interpretation of the electronic states of the alkanes, the structural analogs of the poly(organosllylenes) ( 3, 6). The basic assumption... 

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