Synthesis and characterization of 1,7-disubstituted and 1,6,7,12-tetrasubstituted perylenetetracarboxy-3,4:9,10-diimide derivatives (original) (raw)
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The Journal of …, 2009
A series of 1,7-bis(arylethynyl)-N,N′-bis[2,6-diisopropylphenyl]perylene-3,4:9,10-bis(dicarboximide)s has been obtained from Sonogashira coupling of the 1,7-dibromoperylene-3,4:9,10-bis(dicarboximide) with p-substituted phenylacetylenes in which the p-substituents include π-donors (dialkylamino, diarylamino, p-(diarylamino)phenyl, alkoxy) and π-acceptors (diarylboryl, p-(diarylboryl)phenyl). The bis(arylethynyl)-substituted chromophores all show two reversible molecular reductions and are all slightly more readily reduced than unsubstituted perylene-3,4:9,10-bis(dicarboximide)s with the electrochemical potentials being rather insensitive to the π-donor or acceptor nature of the aryl group. The amine derivatives also show reversible molecular oxidations. The UV-vis spectra of the chromophores with alkoxy and boryl substituents show red-shifted absorptions relative to unsubstituted perylene diimides with discernible vibronic structure. In contrast, the lowest energy absorptions of the amino derivatives are broad and structureless, suggesting donor-to-acceptor charge-transfer character. Transient absorption spectra for the amine derivatives were interpreted in terms of ultrafast charge separation, followed by charge recombination on a time scale of ca. 80-2000 ps. Two compounds were also synthesized in which an additional stronger, but more weakly coupled, donor group is linked by a nonconjugated bridge to the p-amine donor, to investigate the effect on the charge recombination lifetimes; however, the lifetimes of the charge-separated states, ca. 150 and 1000 ps, were within the range observed for the simple amine systems. Finally, the two-photon absorption properties of three bis(arylethynyl)substituted derivatives were investigated, along with those of 1,7-di(pyrrolidin-1-yl)-N,N′-bis[2,6-diisopropylphenyl]perylene-3,4:9,10-bis(dicarboximide). As with other perylene-3,4:9,10-bis(dicarboximide)s and related species, strong two-photon absorption (>1000 GM) was observed for three of these species close to the one-photon absorption edge; however, an additional feature (100-500 GM) was also observed at longer wavelength. An example with (p-aminophenyl)ethylnyl substituents showed a qualitatively different twophoton spectrum with a cross-section >500 GM being observed over a broad wavelength range. Figure 1. Generic structure of a PDI including two structures compared with the alkyne derivatives discussed in this paper.
Regioisomers of Perylenediimide: Synthesis, Photophysical, and Electrochemical Properties
The Journal of Physical Chemistry B, 2012
A series of conjugation extended donor−acceptor 1,6and 1,7-regiomers of perylenediimide were synthesized, separated, and characterized. The photophysical, electrochemical, and thermal properties of these compounds were investigated and compared. The absorption spectra of 1,6-substituted PDI showed blue shift as compared to its 1,7-substituted PDI. At the same time, the emission spectrum showed no significant differences among the regiomers. Both 1,6-and 1,7regiomers were thermally stable up to 450°C and showed different melting and crystallization transitions. The electrochemical studies did not show significant differences in oxidation and redox potentials owing to similar HOMO/LUMO gap of 1,6-and 1,7-regiomers, which is also supported by theoretical calculations. Comparison of properties of a series of 1,6-or 1,7-substituted PDIs showed significant differences. Such regiomerically pure compounds can offer certain advantages in applications, which are currently being investigated.
Dyes and Pigments, 2006
Exploration of optoelectronic properties of novel phosphorus-embedded π-conjugated compounds would provide us with fundamental information about the design of hitherto unknown electroactive organic materials. Herein, detailed photophysical and electrochemical profiles of a series of benzene-cored diketophosphanyl compounds were investigated with steady-and time-resolved spectroscopic and spectroelectrochemical techniques. The comparative studies revealed the impact of phosphorus and nitrogen atoms on their triplet energies and on the behaviour of electrochemical processes to form radical species. 1. Introduction The creation of novel main-group element-embedded π-conjugated organic compounds and their building blocks them is vitally important for the development of the next-generation electroactive materials for organic light-emitting diodes (OLEDs), organic photovoltaics (OPVs) and organic field effect transistors (OFETs) [1-4]. Particularly, much attention has been paid to phosphorus-containing π-conjugated compounds, because their optoelectronic properties (e.g., HOMO/LUMO energies, photo-absorption/emission properties, etc.) can be effectively tailored through (C-P)σ*-π* electronic interaction and chemical P-functionalization [5-9]. Making use of their unique physicochemical properties, phosphorus-containing π-conjugated compounds have been utilized as high triplet-energy host materials for OLEDs [10,11] and as emitters [12] in the field of optoelectronics.
Optical and Self-Assembly studies of some New Perylene Tetracarboxylic Diimides
DJ journal of engineering chemistry and fuel, 2016
Two new symmetrical Perylene Tetracarboxylic Diimides (PTCDIs) namely HA-PTCDI and DA-PTCDI were synthesized by the condensation reaction of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) and with suitable anilines in molten imidazole. Optical and emission properties of both the synthesized compounds at various concentrations in chloroform were studied by using absorption and fluorescence studies respectively. The varying rod like morphological features of the synthesized compounds was observed by using scanning electron microscopy, optical microscopy and phase microscopy techniques. Computational studies such as NMR shielding analysis, molecular electrostatic potential (MEP) analysis and natural bonding orbital (NBO) analysis were performed in order to get a better understanding of the synthesized compounds.
Organic chemistry frontiers, 2016
A family of novel unsymmetrical "peri"-substituted perylene-3,4,9,10-tetracarboxylic acid derivatives (5-10), with 1,6,7,12tetrachloro-substitutents at the bay-positions, has been synthesized. Subsequently, their redox and optical properties have been explored with the intent of unveiling opto-electronic characteristics of these newly synthesized compounds. To synthesize these new compounds, pure 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic tetra-n-butylester (4) has been employed as the precursor and the structural modifications have been carried out exclusively at the "peri" positions in an efficient manner. The two synthons prepared in this work, 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic di-nbutylester monoanhydride (5) and 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic monoimide monoanhydride (8), are extremely valuable and versatile starting materials as they possess free anhydride functionality at the "peri" position in addition to the 1,6,7,12-tetrachloro-bay-substituents. Finally, the conventional methodology for the synthesis of 1,6,7,12tetraphenoxy-bay-functionalized perylene bisimides and perylene bisbenzimidazoles has been modified to make it faster and more convenient.
The influence of substituents of perylenediimides on their spectroscopic properties
Journal of Luminescence, 2018
The influence of substituents of newly synthesized perylenediimides on their spectral properties and excited state relaxation has been studied by means of steady-state and timeresolved spectroscopy and quantum chemical calculations. Substituents at the perylene core cause broadening and shift of the absorption and fluorescence bands and also reduce the fluorescence quantum yield. Organic 4-tert-butylphenoxy substituents reduce the fluorescence yield by tens of percent by slightly reducing the oscillator strength of the radiative transition and by significantly increasing the non-radiative decay rate. We attribute both changes mainly to the distortion of the planarity of the perylene core. Bromine substituents reduce the fluorescence quantum yield by up to two orders of magnitude by opening an internal conversion channel.
Optical properties and structural morphology of one-dimensional perylenediimide derivatives
Journal of Luminescence, 2018
Three derivatives of perylenediimide derivatives, namely N,N'-Di(tridecyl)-3,4,9,10 perylenetetracarboxylic diimide (DT-PDI), N,N'-dipentyl-3,4,9,10-perylene tetracarboxylic diimide (DP-PDI) and N,N'-Di(dihexyle)-3,4,9,10-perylene tetracarboxylic diimide (DH-PDI) differ in their side-chain substitution have been studied to examine the effect of the substituents on the optical properties and structural morphology in the self-assembly. Due to the different side-chain, the self-assembly of these molecules results in totally different optical properties and structural morphologies, as confirmed from the steady-state absorption and fluorescence, time resolved fluorescence, and scanning electron microscopy (SEM) techniques. The collected results confirmed the formation of onedimensional (1D) nanowires in the case of short linear side chain, chunky aggregates in the case of long linear substituted side chain, and zero-dimensional (0D) nanospheres with the branched substituted side chain.
Perylene Monoimide as a Versatile Fluoroprobe: The Past, Present, and Future
Organic Materials
Perylene dyes have transcended their role as simple colorants and have been reinvigorated as functional dyes. Based on the substitution at the peri-position by six-membered carboxylic imides, the perylene family is principally embellished with perylene diimides (PDIs) and perylene monoimides (PMIs). Perylene dyes are widely acclaimed and adorned on account of their phenomenal thermal, chemical, and photostability juxtaposed with their high absorption coefficient and near-unity fluorescence quantum yield. Although symmetric PDIs have always been in the limelight, their asymmetrical counterpart PMI is already rubbing shoulders, thanks to the consistent efforts of several scientific minds. Recently, there has been an upsurge in engendering PMI-based versatile organic architectures decked with intriguing photophysical properties and pertinent applications. In this review, the synthesis and photophysical features of various PMI-based derivatives along with their relevant applications in ...