Synthesis, electrochemical, and spectroscopic properties of soluble perylene monoimide diesters

Perylene derivatives are an important class of n-type semiconductors. With the exceptions of bay-substituted and N-swallow-tail alkyl/tert-butyl substituted derivatives, most perylene diimides are insoluble. The recently reported perylene tetraesters are highly soluble, but are less electron-deficient. In this paper, a series of perylene monoimide diesters have been synthesized, which have good solubility and acceptable electron-accepting property due to the introducing of imide and ester groups in one perylene molecule. Their electrochemical properties and structural ordering were examined by cyclovoltammetry and X-ray diffraction technique, respectively. Their absorption and emission spectra are reported and discussed.     

Crystal Growth and Characterization of Fluorinated Perylene Diimides

One-dimensional crystals of fluorinated perylene diimides were achieved by the self-assembly of them via solvent-nonsolvent exchanging.The π-conjugated fluorinated perylene diimides were assembled into highly-ordered nanostructures of well-defined morphologies in organic solvents due to the π-π interaction between the aromatic cores.It was found that with more introduced F atoms,perylene diimides showed remarkably improved solubility and thus were much easier to grow into crystals,due to the increased polarity induced by the strong electron-withdrawing F group.More importantly,single crystal of N,N＇-diperfluorophenyl-3,4,9,10-perylenetetracarboxylic diimide（DPFPP）was obtained,and the unit cell-dimensions of triclinic structure were determined by the selected area electron diffraction（SAED） pattems to be a=0.712 nm,b=1.072 nm,c=2.914 nm,a=97.0°,β=89.6°,γ=93.4°.Owing to most of the longest c-axis orienting nearly vertically to the long axis of the needle crystal,the molecular planes are expected to be vertical to the needle axis.     

Perylene-3,4,9,10-tetracarboxylic acid diimides: synthesis, physical properties, and use in organic electronics

Perylene-3,4,9,10-tetracarboxylic acid diimides (perylene diimides, PDIs) have been used as industrial pigments for many years. More recently, new applications for PDI derivatives have emerged in areas including organic photovoltaic devices and field-effect transistors. This Perspective discusses the synthesis and physical properties of PDI derivatives and their applications in organic electronics.     

Curved Perylene Diimides Fused with Seven-Membered Rings

Curved perylene diimides fused with seven-membered rings have been synthesized using a regioselective bay-functionalization method and Pd-catalyzed intramolecular C−H/C−Br coupling reaction. X-Ray analysis and temperature-dependent NMR spectroscopy revealed the curved molecular structure with a certain degree of conformational flexibility. The curved and expanded π-conjugation altered the electronic properties while retaining the intrinsic properties of the parent perylene diimide. Despite the absence of solubilizing N-substituents, the curved perylene diimides showed sufficient solubility for application in solution-processed organic photovoltaic devices. The devices showed superior performance with a power conversion efficiency of up to 2.76% due to suppressed charge recombination. Our detailed investigations suggest that the introduction of a curved structure enables the removal of the bulky N-substituents, which is an effective way to achieve a thin-film morphology suitable for photoelectric conversion.     

Rh(III)-Catalyzed One-Step Synthesis of ortho-Alkynylated Perylene Imide Dyes: Optical and Electrochemical Properties of New Derivatives

A one-step Rh-catalyzed site-selective ortho-C−H alkynylation of perylene as well as naphthalene mono- and diimides is reported. A single step regioselective access to ortho-C−H alkynylated derivatives of these ryleneimides not only increases the step economy of the ortho-functionalization on these dyes but also provides a quick access route towards highly functionalized dyes that have potential optoelectronic applications. Increased solubility of tetra(triisopropylsilyl)acetylenyl PDIs in organic solvents greatly enhances their utility for further derivatization.     

A facile route to water-soluble coronenes and benzo[ghi]perylenes

Click reactions at the bay-position of perylenes and a new route to benzo[ghi]perylenes and coronenes are presented. Irradiation with light leads to an electrocyclic reaction of the newly formed triazole ring(s) with the neighbouring bay-positions of the perylene core and after oxidation by air, the benzo[ghi]perylenes and coronenes are obtained. By using Newkome dendrimers as substituents for perylene diimides (PDIs), water solubility can be achieved after removal of the tert-butyl protecting groups. The aggregation and optical properties of the bay-functionalised PDIs, benzo[ghi]perylenes and coronenes are investigated by absorption and fluorescence spectroscopy.     

Columnar benzoperylene-hexa- and tetracarboxylic imides and esters: synthesis, mesophase stabilisation and observation of charge-transfer interactions between electron-donating esters and electron-accepting imides

Benzo[ghi]perylene 1,2,4,5,10,11-hexacarboxylic trialkylimide and dialkylimido-dialkyl ester derivatives, displaying a thermodynamically stable hexagonal columnar liquid-crystalline phase at room temperature, have been obtained by the use of previously unexplored chiral racemic α-branched alkylimide functions. One of the trialkylimides described here is the first room temperature columnar solely oligo-alkylimide-substituted arene, and thus constitutes a prototype case of self-assembling organic acceptor materials. As the related hexacarboxylic hexaesters are found to exhibit only a weak tendency to form columnar mesophases, benzo[ghi]perylene 1,2,5,10-tetracarboxylic tetraalkyl esters have been synthesized by regioselective oxidative Diels-Alder addition of maleic anhydride to 3,10-dicyanoperylene, and a room temperature hexagonal columnar mesophase was obtained with branched alkyl chains. The acceptor-type electronic properties of the tri- and diimides have been found to be considerably more pronounced than those of the hexa- and tetracarboxylic esters, and to approach those of the prototype acceptor material C(60). The formation of bathochromically absorbing donor-acceptor complexes was observed with a di- or triimide as acceptor and a tetraester as donor, but not with a hexaester as donor. Exploiting the non-negligible differences in reduction and oxidation potentials between all four types of materials, the minimum HOMO energy difference necessary for charge-transfer-complex formation has been determined to lie between 0.29 and 0.35 eV.     

Synthesis and self‐organization properties of copolyurethanes based on perylenediimide and naphthalenediimide units

A series of perylene and naphthalene diimide‐containing random copolyurethanes with different ratios of perylene/naphthalene diimide content was synthesized and characterized. Copolymerization improved the solubility of these rigid aromatic diimides, and the copolymers were soluble in common organic solvents like chloroform, tetrahydrofuran, and so forth. The absorption spectra of perylene‐based copolymers showed a red‐shifted peak at a wavelength of 557 nm corresponding to J‐type aggregates. For naphthalene copolymers, the quenching of fluorescence at higher naphthalene incorporation suggested the presence of aggregates because of the extensive π‐π stacking of the aromatic core. FTIR spectroscopic analysis showed that the hydrogen bonding tendency of the polymer decreased with increase in perylene/naphthalene incorporation. The fluorescence spectra of the perylene polymers were exactly a mirror image of the absorption spectra. The fluorescence spectra of the naphthalene polymers at higher naphthalene incorporation showed a red‐shifted excimer like emission peak, which was assigned as static excimers based on their excitation spectra. These polymers could exhibit two types of secondary interaction modes, namely, hydrogen bonding (via urethane linkage) and π‐stacking (via aromatic perylene or naphthalene units) thus highlighting the importance of polymer design in inducing self‐organization at both low and high incorporation of the rigid bisimide moieties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1224–1235, 2009     

New hydrosoluble perylene and coronene derivatives

Several lipophilic perylene and coronene derivatives, employed mainly as liquid crystalline dyes are known and their synthesis has been widely studied. We have applied an analogue strategy using hydrophilic substituents to obtain highly water soluble perylene diimides (4) and a new hydrosoluble coronene derivative (CORON, 6), whose molecular features appear particularly suitable for inducing G-quadruplex DNA structures and inhibiting human telomerase.     

Towards highly fluorescent and water-soluble perylene dyes

A systematic approach towards highly fluorescent, water-soluble perylene-3,4:9,10-tetracarboxylic acid diimide chromophores is presented. Water solubility was introduced first through the attachment of four hydrophilic substituents onto the bay region of the perylene dye. Positively and negatively charged groups were then applied to the chromophore, and their number and their distance from the aromatic scaffold were systematically varied. To suppress aggregation, the chromophore was further isolated within a dendritic shell. Such variation of structural features and a thorough investigation of the resulting optical properties facilitated the first synthesis of perylene-3,4:9,10-tetracarboxylic acid diimides combining the properties of water solubility and fluorescence quantum yields (FQYs) close to unity, which makes them attractive as high-performance fluorescence probes in aqueous media.     

Columnar Liquid‐Crystalline Dibenzopentacenodithiophenes by Photocyclization

The twofold glyoxylic Perkin reaction of perylene‐3,9‐diglyoxylic acid with thiophene‐diacetic acid followed by oxidative photocylization and reaction with α‐branched primary alkylamines yields columnar liquid‐crystalline diimides with two sulfur atoms in the condensed arene system. A broad temperature range of the hexagonal columnar mesophase is induced by racemic doubly branched alkyl chains. The HOMO and LUMO energy levels of these thiophene‐derived diimides qualify them as electron donors with respect to perylene diimides.     

氟代位置对苝酰亚胺聚集态结构和电子传输性能的影响

合成了三种新型的有机电子受体: N,N'-二(2-氟代苯基)-3,4,9,10-苝四羧基二酰亚胺(D2MFPP)、N,N'-二(3-氟代苯基)-3,4,9,10-苝四羧基二酰亚胺(D3MFPP)和N,N'-二(4-氟代苯基)-3,4,9,10-苝四羧基二酰亚胺(D4MFPP). 利用元素分析、傅立叶变换红外(FTIR)等方法表征了它们的分子结构, 用紫外-可见光吸收光谱(UV-Vis)、X射线衍射(XRD)和原子力显微镜(AFM)等手段研究了氟代位置对苝酰亚胺薄膜聚集态结构的影响, 发现氟代使苝酰亚胺的聚集态发生变化, 且不同位置的氟代对其影响也不一样. 除了分子结构的影响, 外场条件也会产生很大的作用. 通过制备场效应晶体管研究了其电子传输性能, 发现氟代后器件的空气稳定性有明显提高.     

可溶性苝四羧酸二酰亚胺发光材料的合成及表征

以苝四酸酐为原料合成了1,7-二溴-3,4,9,10-苝四酸酐(PeryBr₂)、N,N′-二(十二烷基)-1,7-二溴-3,4,9,10-苝四羧酸二酰亚胺(DD-PeryBr₂)和N,N′-二(十二烷基)-1,7-二对叔丁基苯氧基-3,4,9,10-苝四羧酸二酰亚胺(DD-PeryBp₂) 3种苝四羧酸二酰亚胺类化合物,并对其结构和性能利用紫外-可见吸收光谱、傅立叶红外光谱、核磁共振、质谱、热分析和荧光光谱测试技术进行了表征和测试。 结果表明,DD-PeryBp₂能很好的溶于甲苯、氯仿、四氢呋喃等常用有机溶剂。 紫外可见最大吸收波长和荧光最大发射波长分别为548和576 nm。 DD-PeryBp₂具有很好的热稳定性,质量损失5%时的温度为433 ℃。     

1,1'-Binaphthol annulated perylene diimides: Aggregation-induced emission enhancement and chirality inversion

Aggregation-induced emission enhancement and aggregation-induced chirality inversion are two individual phenomena for the enantiomerically pure organic dyes in the aggregates. Herein we reported for the first time that these two interesting phenomena could be observed simultaneously in the aggregated states of enantiomerically pure S/R-1,1’-binaphthol annulated perylene diimides, in which two perylene diimides moieties were bridged by S/R-1,1’-binaphthol(BINOL) at the bay positions. Owing to the...     

The impact of vertical π-extension on redox mechanisms of aromatic diimide dyes

The impact of vertical π-extension on redox mechanisms of aromatic diimides in the organic lithium-ion batteries have been carefully studied by a combined experiment and theoretical analyses.     

Regioselective Functionalization of Core‐Persubstituted Perylene Diimides

Regioselective functionalization of core per‐substituted perylene diimides has been achieved efficiently based on a new versatile building block, named tetrabromotetrachloro‐perylene‐3,4:9,10‐tetracarboxylic acid dianhydride (Br₄Cl₄‐PTCDA), which affords a series of novel chromophores with impressive optoelectronic properties. Direct palladium‐catalyzed fourfold intramolecular ring fusion affords successfully unique propeller‐shaped biscarbazole[2,3‐b]carbazole diimides with six annulated rings.     

Perylene monoanhydride diester: a versatile intermediate for the synthesis of unsymmetrically substituted perylene tetracarboxylic derivatives

A soluble perylene monoanhydride diester has been designed and synthesized. It was successfully utilized as an efficient intermediate for the synthesis of the first unsymmetric perylene tetracarboxylic tetraester and a series of unsymmetric perylene diester monoimides in good to excellent yields. Its application in synthesis of unsymmetric perylene diimides was also demonstrated. Availability of such a versatile intermediate would enable the convenient integration of perylene tetracarboxylic tetraesters and perylene biester monoimides into intricate functional molecular systems.     

Solubility and Crystallizability: Facile Access to Functionalized π‐Conjugated Compounds with Chlorendylimide Protecting Groups

Functional π‐conjugated molecules are relevant for the preparation of new organic electronic materials with improved performance. However, their synthesis is often rendered difficult by their inherently low solubility, and the permanent attachment of solubilizing groups may change the properties of the material. Here, we introduced the chlorendylimidyl moiety as a new temporary protecting group for the straightforward large‐scale synthesis of protected quarter‐, sexi‐, octathiophene, and perylene bisimide diamine and dicarboxylic acid derivatives. The obtained chlorendylimides and chlorendylimidyl active esters were highly soluble in organic solvents, and optical spectroscopy confirmed the low tendency of the compounds to aggregate in solution. At the same time, they could be conveniently purified by recrystallization or precipitation. Single‐crystal X‐ray structures obtained for most compounds showed supramolecular motifs highlighting the role of the rigid, polychlorinated chlorendyl moieties in their crystallization. The obtained protected diamine and dicarboxylic acid derivatives were easily deprotected and converted into various amide‐substituted oligothiophenes and perylene bisimides that are of interest as new functional materials for organic electronic thin film or nanowire devices.     

The impact of vertical π-extension on redox mechanisms of aromatic diimide dyes

Aromatic diimide dyes are an attractive class of redox-active organic molecules for lithium-ion batteries, whose battery performances (stabilities, conductivities and cyclicities) are strongly dependent on the sizes of their π-systems. However, due to the different Clar’s structures possessed, three vertically π-extended aromatic diimides, namely, naphthalene diimide (two one-electron reductions), perylene diimide and terrylene diimide (two one-electron reductions), exhibit different electronic redox mechanisms when served as cathode materials in organic lithium-ion batteries. Herein, we have studied carefully the different electrochemical characteristics of the three aromatic diimides through experimental and theoretical calculations. Their battery present different shape of charge/discharge curves resulting from stability of their reduction state during charge/discharge process. Terrylene diimide shows better cycle and rate capacities than those of naphthalene diimide and perylene diimide, which could be attributed to the more energies released during terrylene diimide combining with lithium ions than those of other two diimides.     

The Photostability of Two Optical Materials Based on Perylene Diimide Substituted by Different Aromatic Groups at the Bay Area

The perylene diimide substituented by thiophene rings at bay area shows photoactivity and can be used as a photo sensor, but another one substituented by mestylene groups is photostable. The single crystal of 1,7‐mesitylene perylene diimide was obtained. X‐ray diffraction data of the crystal revealed that the plane of the perylene core was hardly twisted by introduction of mesitylene groups. These mestylene groups are like clips maintaining the planarity of the perylene core. Density functional theory calculation was applied to study the difference of photophysical and photochemical properties. The discovery is valuable for design guidance of perylene diimides.