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Fluorene (Fl) is a polycyclic aromatic compound, which received its name due to strong violet fluorescence which arise from high conjugated planar -electron system.

1.1 Characterization, stability and phase behavior

GPC with calibration against polystyrene standard is common method for estimation of the molecular weight of PF Mn of PF ranges from 10,000 to 200,000 with PDI 1.5 3, using polystyrene as standard. Generally, fluorene homo- and co-polymers show excellent thermal stability: the decomposition temperature (Tdec) of many PF exceeds 400 C (according to TGA analysis under inert atmosphere).

Poly(9,9-dihexylfluorene) (PDHF, comp 187) is generally considered amorphous. Some PFs with larger alkyl side chains dioctyl (PFO, comp 188) or bis(2-ethylhexyl) (PEHF, Comp 189) show liquid crystal behavior, opening a possibility to fabricate polarized LEDs.

PFO is clearly crystalline with a melting point around 150 C. Nanoscale crystallinity of PFO was demonstrated by X-ray diffraction (XRD) experiments

1.2 Optical and Electronic Properties

1.3 General method in synthesis of PF homopolymer

The first synthesis of poly(9,9-dialkylfluorene) with long- chain solubilizing hexyl groups was carried out by Yoshinos group via oxidative coupling reaction using ferric chloride in chloroform.

This result in polymers with relatively low molecular weight (Mn up to 5,000) A serious drawback of this synthesis method was also a significant amount of residual metal impurities, which dramatically affected the PLED performance

The next step towards soluble PF as material for PLEDs, was an application of Yamamoto

- Polymer has high molecular weight (Mn = 94,000; PDI = 2.3) - Although Ni catalyzed reaction allowed improvement of the regiospecificity and minimization of cross-linking and miss-linking reaction as compared to FeCl3 oxidation method, it employs large amount of metals (Ni, Zn) during the synthesis and resulting polymer should be carefully purified from the metal impurities. - Thus, whereas relatively high MW Mn 94,000 can be achieved for PF comp.190, containing hydrophilic 3,6-dioxaheptyl substituents, in the cases of various alkyl substituents the MW are limited 14,000 60,000

2.4 The problem of pure blue emission in PFs: excimer/aggregate formation or fluorenone defects?

2.5 Aromatic ring-substituted PF

2.6 Side-chain modification in PF

2.7 End-capped PFs

The very first and obvious reason for introducing the end groups, terminating the polymer chain was to replace reactive functionalities (halogen, boronic acid or metalorganic group), which can quench the fluorescence or decrease the stability of the material. Secondly, varying the feed ratio of the end-capping reagent, one can control the MW of the polymer. Third important reason for end-capping is tuning the optoelectronic properties of the polymer by electronically active end-capper.

Enthracene end-capper

Triarylamine end-capper

Silsesquioxane end-capper Benzocycloburene end-capper

Benzocycloburene end-capper