Synthesis and properties of fluorene-oligothiophenes perylenediimide triads and their electropolymerizations

Abstract

A series of novel donor-acceptor-donor triads, namely PFTn (n ¼ 0-4), consisting of fluoreneoligothiophenes (FTn) as a donor and perylenediimide (PDI) as an acceptor were synthesized and characterized. The chemically bonded electron donor and acceptor chromophores in the triads were found to be independent. These triads showed a strong intramolecular photo-induced electron transfer (PET) between both chromophores, which gave rise to a quasi-quantitative fluorescence quenching of both PDI and FTn moieties. Distinctively, a reverse energy transfer from the acceptor PDI to the donor FTn induced a strong fluorescence emission from the FTn moieties in the triads PFT3 and PFT4. The PFTn (n ¼ 1-3) triads were proven to undergo an electrochemical oxidative coupling reaction and become electropolymerizable materials to form polymer plastic films (poly(PFTn)), while PFT4 proved to be an electrochemically stable molecule. Experimental sectionGeneral procedure 1 H and 13 C nuclear magnetic resonance (NMR) spectra were recorded on a Bruker AVANCE 300 MHz spectrometer with tetramethylsilane as the internal reference using CDCl 3 as the solvent in all cases. Infrared (IR) spectra were measured on a Perkin-Elmer FTIR spectroscopy spectrum RXI spectrometer as a KBr disc or thin film obtained from electropolymerization. Ultraviolet-visible (UV-vis) spectra were recorded as a dilute solution in spectroscopic grade dichloromethane or as a thin film obtained from electropolymerization on a Perkin-Elmer UV Lambda 25 spectrometer. Photoluminescence spectra and the fluorescence quantum yields (F F ) were recorded with a Perkin-Elmer LS 50B luminescence spectrometer as a dilute solution in

Recent advances in conjugated polymer energy storage

“…12,69,196 The Reynolds group has circumvented the poor polymerizability of n-type monomers by sandwiching an electron poor n-type heterocycle between two electron rich heterocycles to form a donor-acceptor polymer. 47,197 These n-dopable polymers were examined in symmetric supercapacitors using non-aqueous electrolyte. It was found these devices could attain operating voltages as high as 2.5 V and energy densities of $13 Wh/kg although they experienced a loss of electrochemical activity after 200 cycles.…”

A Thiophene-Containing Conductive Metallopolymer Using an Fe(II) Bis(terpyridine) Core for Electrochromic Materials

“…52 Thus, it seems reasonable to assume that the thiophenecontaining metal-bis(terpyridine) complex underwent oxidative electropolymerization by linking the α-carbons of the outermost thienyl groups of each complex to the outermost αcarbons of the neighboring complex, as illustrated in Scheme 2. 53 For the electropolymerization of Fe(L2) 2 on the ITO surface, the linear increase of redox current at E 1/2 = 0.77 V (Figure 3) indicates that the amount of deposited polymer on the ITO surface was increased with successive CV scans. The irreversible redox behavior at 1.12 V can be attributed to the oxidation of the bithiophene moiety.…”

“…The electrochemical polymerization mechanism of polythiophene is known to display a 95%+ preference for α,α-coupling . Thus, it seems reasonable to assume that the thiophene-containing metal-bis­(terpyridine) complex underwent oxidative electropolymerization by linking the α-carbons of the outermost thienyl groups of each complex to the outermost α-carbons of the neighboring complex, as illustrated in Scheme …”

Golden Age of Fluorenylidene Phosphaalkenes–Synthesis, Structures, and Optical Properties of Heteroaromatic Derivatives and Their Gold Complexes

“…The construction of extended π-conjugated frameworks can be rationally based on the combination of different conjugated aromatic building blocks. , The combination of suitable donor and acceptor units often leads to interesting optical and electronic properties. , For example, 9,9-dialkylated fluorene derivatives (Figure , I ) have been used extensively as efficient π-spacers in the construction of photoluminescent materials, dyes for dye-sensitized solar cells, and other optoelectronic applications. − The dialkylation significantly enhances solubility and has an influence on molecular packing, e.g., π-stacking; however, it does not significantly alter the optical and electronic properties compared to the parent 2H-fluorene . Similarly, dibenzoheteroles of group 14 to 16 have found widespread use as optoelectronic materials. − Fluorene cores can also be functionalized with thiophene or benzothiophene moieties to provide diverse optoelectronic properties such as solvatochromism, tunable emission, etc. − …”