Synthesis and Modification of Terrylenediimides as High‐Performance Fluorescent Dyes

Abstract

Two new synthetic approaches to terrylenediimides, highly photostable fluorescent dyes, are described. For the first time terrylenediimide has been synthesised in a straightforward procedure that makes large quantities available. The second route includes an efficient cross-coupling reaction followed by a cyclodehydrogenation. Monofunctionalisation of the imide structure allows terrylenediimides now to be coupled with a variety of compounds, for example, by Suzuki cross-coupling, which can lead to an array of terrylenediimides with new functional groups such as hydroxy, amino, or carboxy groups needed to link up with other molecules. The functionalisation in the bay region is used to tune the properties of terrylenediimides and extend the range of applications, for example, by introducing water solubility. These tetrasubstituted terrylenediimides offer, depending on the substituents used, exciting features such as good solubility in common organic solvents, water solubility, or NIR absorption.

Perylene Imides for Organic Photovoltaics: Yesterday, Today, and Tomorrow

“…Additionally, 16 may also be obtained by direct coupling reaction of 12 and non-substituted naphthalene monoimide under drastic base-induced cyclization. [20] Linking 13 with amine, such as diphenylamine, generates a push-pull type perylene compound that can be used for photovoltaics, especially dye-sensitized solar cells because the donor (diphenylamine) and the acceptor (imide) substituted perylenes show a bathochromically shifted absorption as well as strong intramolecular charge transfer which is favorable for high efficiency devices. [2] Furthermore, in order to improve the solubility of PMI 13, tribromo-PMI 14 gives the possibility to first react the 1,6-positions of perylene core and then decorate the 9-position.…”

Amino-substituted rylene dicarboximides and their quinoidal charge delocalization after deprotonation

“…N-(2, 6-diisopropylphenyl)-4-bromo-naphthalene 1,8-dicarboximide (6), N-(2, 6-diisopropylphenyl)-9-bromo-perylene 3, 4-dicarboximide (7), N-(2, 6-diisopropylphenyl)-1,6,9,14-tetrakis(4-(1,1,3,3-tetramethylbutyl) phenoxy)-11-bromo-terrylene 3,4-dicarboximide (8) and N-(2, 6-diisopropylphenyl)-1,6-bis (4-(1,1,3,3-tetramethylbutyl)phenoxy)-13-bromo-quarterrylene 3, 4-dicarboximide (9) were synthesized as previously described [1][2][3] . Column chromatography was performed on silica gel (Geduran Si 60 , Merck).…”

The Synthesis of Azaperylene-9,10-dicarboximides

“…Moreover, we anticipated that the rigidity of 1-azaperylene, combined with its lack of solubilizing groups, would lead to complexes of poor solubility. Instead, we envisioned that (a) introduction of an electron-withdrawing imide moiety to the azaperylene skeleton would allow the use of a comparatively-mild, base-promoted cyclization procedure 11,12 to synthesize the desired azaperylene imides and that (b) introduction of bulky substituents at the N-imide position would greatly improve the solubility of the chromophore. Additionally, the resulting azaperylene imide chromophore would have bathochromically shifted absorption and emission spectra relative to the cyan-emitting 1-azaperylene.…”

“…In order to cyclize 7, 8 and 10, the base-promoted cyclization procedures described in the syntheses of extended rylene diimide chromophores were investigated. 11,12 In these examples, it is thought that nucleophilic attack of an arylide anion initially generates the leuco form of the chromophore (12), which subsequently oxidizes to form the rylene skeleton (Scheme 2). 16 Compounds 7 and 8, which are both precursors to azaperylene imide 3, differ only in the position at which the naphthalene imide and isoquinoline rings are linked.…”