Introduction of an Arylethynyl Group onto an Anthracene Bisimide Core for Molecular Design of New π-Conjugated Compounds

Abstract

Novel ethynylated anthracene bisimide (ABI) derivatives were synthesized by Sonogashira and Stille couplings, and the electronic spectra of the new compounds were compared with those of molecules with related structures. The absorption spectrum and the electrochemical data of the ABI with a 9-anthrylethynyl group suggested weak electronic interactions between the donor anthracene unit and the acceptor ABI unit.As electron-deficient moieties, aromatic bisimides have been attractive building units for the molecular design of new π-conjugated functional materials.1 In particular, perylene bisimides and naphthalene bisimides have been extensively applied to the development of new organic devices 2 such as organic light-emitting diodes, 3 organic field-effect transistors (OFETs), 4 and organic photovoltaics. 5,6 Anthracene-2,3:6,7-bisimides (ABIs) are also promising candidates for the construction of various functional molecules.7 ABI derivatives with 1,5-diphenyl and 9,10-dicyano groups have been utilized as chemical sensors 8 and OFET materials, 9 respectively. In general, the electronic properties of anthracene moieties are considerably influenced by substitution with arylethynyl groups.10 However, to the best of our knowledge, no ABI derivatives having acetylene substituents have yet been reported in the literature. Recently, we reported that a donoracceptor array consisting of a perylene bisimide core and a 9-anthrylethynyl group showed interesting spectroscopic properties due to charge-transfer interactions.11 Therefore, we designed a new donoracceptortype ABI derivative 1 having a 9-anthrylethynyl group at the 9 position, in which the ABI unit serves as a terminal acceptor unit (Figure 1). We herein report the synthesis and spectroscopic data of ABI derivative 1 and its analogue 2 and the results of a comparison of their photophysical and electrochemical properties with those of the related compounds 3 12 and 4 9 in order to evaluate the π-conjugation.For the synthesis of the target ABI derivatives, 9-Br-ABI 8 was used as a key intermediate for ethynylation by crosscoupling reactions. This precursor was prepared by the Diels Alder approach, as shown in Scheme 1. Durene was first brominated to afford compound 5, 13 which was then further brominated by irradiation with bromine to give heptabromide 6 in a manner similar to a previously known method.7,9 The regioselectivity of the bromination was confirmed by X-ray structural analysis [see the Supporting Information (SI)].14 Reaction of 6 with N-octylmaleimide in the presence of NaI afforded the DielsAlder adduct 7 as a mixture of diastereomers, which was then aromatized by radical bromination followed by elimination. The series of reactions gave compound 8 in 26% overall yield from 6.The Sonogashira coupling of 8 with 9-ethynylanthracene 15 in a conventional manner gave compound 1 as a red solid in 95% yield, while the Stille coupling of bromide 8 with bis(tributylstannyl)ethyne in the presence of [Pd(PPh 3 ) 4 ], as well as LiCl as additive in dioxane gave comp...

Synthesis and Physical Properties of Novel 7, 12-Diaryl-<i>N</i>-phenylbenzo[<i>k</i>]fluoranthene-9, 10-dicarbox- imides

“…[9][10] These findings have prompted organic chemists to develop various new synthetic methods access to dicarboximide compounds. [14][15][16][17] We recently developed an efficient annulation between arene-1, 2-dicarbaldehydes and maleimides [18][19][20][21] by improving the previously reported Haddadin's result. [22] As shown in Fig.…”

Concomitant conformational dimorphism in 1,2-bis(9-anthryl)acetylene

“…1 In this regard, anthracene-based compounds have been especially promising as their stability toward oxidative and photochemical degradation, solubility, processability, and molecular packing lead to desirable optoelectronic properties. 4 The crystal structure of 1 was first reported by Becker et al nearly 30 years ago. 3 Compound 1 has been also used as a reference for comparison to other anthracene-based functional materials.…”

“…3 Compound 1 has been also used as a reference for comparison to other anthracene-based functional materials. 4 The crystal structure of 1 was first reported by Becker et al nearly 30 years ago. 5 That structure, identified as DITBEN in the Cambridge Structural Database 6 revealed an essentially planar, centrosymmetric molecule.…”

Synthesis and Emission Behavior of 1,3-diarylisobenzofuran-5,6-dicarboximides and Their Transformation into Naphthalene-2,3:6,7-bis(dicarboximide)s

“…Arene-dicarboximides can be obtained by several simple ways, such as condensation of anhydride with amine [11,[13][14][15] and Gabriel reaction of N-unsubstituted dicarboximide with alkyl or aryl haide [16][17][18]. Besides, an approach by Diels-Alder reaction via arene-o-quinodimethane or isobenzofuran constructing concomitantly another benzene ring has been reliable [19][20][21][22]. In 1979, Haddadin et al reported an interesting synthetic method, in which o-phthaldehyde (1) reacts with N-phenylmaleimide (3) in the presence of triethylphosphite to give N-phenylnaphthalene-2,3-dicarboximide (2) in a satisfactory yield (62%) [23].…”