The electroluminescence (EL) of isotactic and syndiotactic poly(N-pentenyl-carbazole) (PPK), achieved by coordination polymerization, is studied in order to investigate the interrelation between thepolymer tacticity and theirphysical-chemical properties. The use of these polymers in organic light-emitting diode (OLED) fabrication is also explored. Thermal and x-ray diffraction analyses of PPKs show that the isotactic stereoisomer is semicrystalline, whereas the syndiotactic one is amorphous. Optical analysis of both stereoisomers, carried out on film samples, reveals the presence of two different excimers:'sandwich-like' and 'partially overlapping'. Nevertheless, the emission intensity ratio between 'sandwich-like' and 'partially overlapping' excimers is higher in the isotactic than in the syndiotactic stereoisomer. Using the synthesized polymers as OLED emitting layers, the influence of the polymer tacticity on theEL properties of the device is highlighted. In detail, while blue OLEDs are obtained by using the syndiotactic stereoisomer, OLEDs witha multilayer structure fabricated with the isotactic stereoisomer emit white light. The contribution of three different emissions (fluorescence, phosphorescence and electromer emissions) with comparable intensities to the detected white light is discussed.

Stereoregular polymers like isotactic poly(N‐butenyl‐carbazole) (i‐PBK), isotactic and syndiotactic poly(N‐pentenyl‐carbazole) (i‐PPK and s‐PPK), and poly(N‐hexenyl‐carbazole) (i‐PHK and s‐PHK) are synthesized using the stereospecific homogeneous “single site” Ziegler‐Natta (Z‐N) catalysts: rac‐dimethylsilylbis(1‐indenyl)zirconium dichloride (1)/methylaluminoxane (MAO) and diphenylmethylidene(cyclopentadienyl)‐(9‐fluorenyl)zirconium dichloride (2)/MAO. Catalytic activity is rationalized by density functional theory (DFT) calculations. All synthesized polymers are fully characterized by NMR, thermal, wide‐angle X‐ray diffraction, and fourier transform infrared spectroscopy analysis. Fluorescence measurements on isotactic and syndiotactic polymer films indicate that all polymers give rise to excimers, both “sandwich‐like” and “partially overlapping.” Excimer formation is essentially driven by the polymer tacticity. Isotactic polymers generate both sandwich‐like and partially overlapping excimers, while syndiotactic polymers give rise especially to partially overlapping ones. A theoretical combined molecular dynamics–time dependent DFT approach is also used to support the experimental results. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 242–251

No abstract

No abstract

No abstract