Triarylamine-based polymers

Nishiyama, and co-workers first reported that the catalyst derived from Pd(OAc)2 and (f-Bu)3P effects the C-N bond formation to produce triarylamines in excellent yield [65]. This system also is useful in the coupling of diarylamines and aryl chlorides. Hartwig and co-workers found this protocol optimal for the preparation of triarylamines. The (f-Bu)3P/Pd-catalyst was sufficiently active such that the coupfing of diarylamines and aryl bromides can be performed at room temperature,Eq. (34) [50]. The (f-Bu)3P/Pd-system has been used to produce new triarylamine-based polymers [ 64 a - d]. 

Ma and coworkers [154] synthesized a bipolar luminescent PPV-based polymer 111, which contained both donor triarylamine and acceptor oxadiazole moieties in the backbone. A device fabricated with this polymer (ITO/PEDOT/111/CsF/Al) showed a maximum brightness of 3600 cd/m2 and a maximum luminescent efficiency of 0.65 cd/A (< el = 0.3%), about 15 times brighter and more efficient than the device of the same configuration with a nonoxadiazole polymer 112. 

Amorphous polymers generally do not give high field effect mobilities. However, a poly(triarylamine)-based system was found to have reasonably high hole mobility (0.008 cm /vs) in a field-effect transistor geometry. Most remarkably, the stability of this material is significantly better than poly thiophenes due to its much higher band gap. 

J. S. Kim, R K. H. Ho, C. E. Murphy, A. J. A. B. Seeley, I. Grizzi, J. H. Burroughes, and R. H. Friend. 2004. Electrical degradation of triarylamine-based light-emitting polymer diodes monitored by micro-Raman spectroscopy. Chem Phys Lett 3G1-2-7. 

Triarylamine and carbazole-based low-molar-mass compounds and polymers have been extensively studied for the different applications due to their good hole transport and luminescent properties. ... 

Fast response photorelfactive materials have been described that are based on a bis-triarylamine side chain polymer matrix with a low ionization potential. ... 

The first examples of the use of (NHC)-Pd complexes for the synthesis of poly (triarylamine)s by C-N coupling between a commercial aniline and dihalobi-phenyls were reported by Turner and Navarro using (NHC)-Pd complexes as precatalysts (Figure 4.33) [93]. The use of [(IPr)Pd(allyl)Cl] allowed for the synthesis of the desired polymer requiring a lower catalyst loading than that using the tri-terf-butylphosphine-based system previously reported [94]. The same authors later reported the unprecedented polymerization of aryl dichlorides with primary aryl amines [95]. 

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