Influence of π–π Hyperconjugation Effect on Thermal, Morphological, and Photoelectronic Properties of Non-Conjugated Pyrene Derivatives

In this paper, four pyrene–fluoroene derivatives with conjugated and nonconjugated pyrene substitution were designed and synthesized. In PFP1 and PFP2, there are nonconjugated pyrene substitution on C9 and conjugated pyrene on C2 and/or C7 of the fluorene moiety, and in the control molecules BP1 and BP2, there is only the conjugated pyrene in the C2 and/or C7 of the fluorene core. There is a special π–π hyperconjugation effect between nonconjugated pyrene and the pyrene–fluorene conjugation in the system (PFP1 and PFP2), which means the electron cloud of such two isolated conjugation systems (nonconjugated pyrene group and pyrene–fluorene group) could be delocalized and transferred to each other. Because of delocalization of electron cloud, the molecule size of PFP1 and PFP2 might have been decreased and led to decreased phase transition temperature compared with that of BP1 and BP2. Also due to the electron transfer between the molecules, the intermolecular force between PFP1 and PFP2 has been improved, which is the reason that they are more amorphous than BP1 and BP2. The easy electron transfer also makes the PFP1 and PFP2 show improved hole injection and device performance compared with that of BP1 and BP2.