Study Of Indolinone-dimer And Polycyclic Triindole Derivatives:Syntheses, Structures And Properties

Polycyclic aromatic hydrocarbons (PAHs) have been prominent target in the field of organic optoelectronic materials, because of their unique and excellent electronic transport properties. Nowadays, PAHs are mainly divided into two categories:one is planar polycyclic aromatic hydrocarbons, such as pentacene, pyrene, coronene et al. The other one is "bowl-shaped" polycyclic aromatic hydrocarbons (Buckybowls), such as corannulene, cyclopentacorannulene, buckminsterfullerene (C60) et al. They have been widely applied in carbon nanotubes, solar cells, organic chemical or biological sensors, organic field effect transistors (OFETs), and organic light-emitting diodes (OLEDs). Numerous researchs show that the electron transporting property of buckybowls is better than that of planar polycyclic aromatic hydrocarbons, due to their unique molecular structure-activity relationship.Since the 1970s, transition metal-catalyzed organic reactions have gradually become one of primary means for the growth carbon chain and expansion of the π-conjugated degree in organic synthesis. We designed a series of reactions which was catalyzed by transition metal Fe, Cu, Pd for the activation of C-H and C-X bonds of various reaction substrates. By these methods, the purpose of extending conjugation to improve optoelectronic properties has been achieved.In this paper, starting from aniline derivatives, we utilized Scholl reaction have we obtained indolin-2-one dimer and its chloro-derivatives from indolinone as a precursor. We mainly researched the activities of various coupling reactions, signal-crystal structures of the dimer, and fluorescent behaviors of the dimer to chemical stimuli. We have successfully synthesized a new propeller-shaped polycyclic triindole, whose configuration is between planar polycyclic aromatic hydrocarbons and buckybowls, by Pd-catalyzed coupling to form C-C bonds. The main results are as following:1. Through Scholl oxidation, we synthesized a series of intermolecular coupling dimers, DPI [5,5’-di-(1-phenylindoline-2-one)], and chloride-, dichloride-substituted derivatives, via controlling the different reaction conditions. The crystal structure and the fluorescent behaviors of DPI to stimuli of metal ions have been determined, and the probe mechanism has been elucidated by Density Functional Theory calculation.2. We have successfully synthesized a kind of propeller-shaped polycyclic triindole, Pro-21 (C42H21N3) and Pro-23 (C42H23N3), through the Pd-catalyzed intramolecular coupling dehydrogenation reaction. The two compounds were synthesized for the first time and a novel configuration of PAHs. The crystal structure of TPTI-3Br and its sandwiched phenomenon for solvent molecules have been determined and discussed. The optical characteristics of Pro-21 and Pro-23 were compared with compounds of similar structure. It is worthy to apply on organic opto-electronic devices due to the high fluorescence quantum yield, excellent large π-conjugation and electron-rich nature of Pro-21 (C42H21N3).