3,4,9,10-Perylenetetracarboxdiimides containing perfluoroalkyl substituents

Deyama, Kazuhito; Tomoda, Hideyuki; Muramatsu, Hiroshige; Matsui, Masaki

doi:10.1016/0143-7208(95)00070-4

Cited by 14 publications

(7 citation statements)

References 14 publications

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“…Modification of these substituents changes the manner in which the dications aggregate in solution and in the solid state. This difference in packing has been observed − previously for perylene diimides, where the presence of large substituents on the imide nitrogens limit π···π aggregation without influencing the planarity of the central perylene core. Although substitution on the bay (5, 6, 12, and 13, Figure ) positions of perylene diimides also limits ,− π···π aggregation, this substitution pattern results in conformational twisting of the perylene core.…”

Section: Resultssupporting

confidence: 72%

“…The presence of the two 2,6- i Pr 2 C 6 H 3 groups also increases the solubility of the DAPP 2+ dication in aqueous and polar organic solvents using chloride or hexafluorophosphate anions, respectively, compared to other groups, e.g. , as in the p -MeC 6 H 4 and m -MeC 6 H 4 derivatives, on account of the restricted ability of these dications to aggregate, a phenomenon which is also observed − with the related perylene diimides in organic solvents.…”

Section: Resultsmentioning

confidence: 80%

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Anticancer Activity Expressed by a Library of 2,9-Diazaperopyrenium Dications

et al. 2015

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Polyaromatic compounds are well-known to intercalate DNA. Numerous anticancer chemotherapeutics have been developed upon the basis of this recognition motif. The compounds have been designed such that they interfere with the role of the topoisomerases, which control the topology of DNA during the cell-division cycle. Although many promising chemotherapeutics have been developed upon the basis of polyaromatic DNA intercalating systems, these candidates did not proceed past clinical trials on account of their dose-limiting toxicity. Herein, we discuss an alternative, water-soluble class of polyaromatic compounds, the 2,9-diazaperopyrenium dications, and report in vitro cell studies for a library of these dications. These investigations reveal that a number of 2,9-diazaperopyrenium dications show similar activities as doxorubicin toward a variety of cancer cell lines. Additionally, we report the solid-state structures of these dications, and we relate their tendency to aggregate in solution to their toxicity profiles. The addition of bulky substituents to these polyaromatic dications decreases their tendency to aggregate in solution. The derivative substituted with 2,6-diisopropylphenyl groups proved to be the most cytotoxic against the majority of the cell lines tested. In the solid state, the 2,6-diisopropylphenyl-functionalized derivative does not undergo π···π stacking, while in aqueous solution, dynamic light scattering reveals that this derivative forms very small (50–100 nm) aggregates, in contrast with the larger ones formed by dications with less bulky substituents. Alteration of the aromaticitiy in the terminal heterocycles of selected dications reveals a drastic change in the toxicity of these polyaromatic species toward specific cell lines.

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Section: Resultssupporting

confidence: 72%

Section: Resultsmentioning

confidence: 80%

Anticancer Activity Expressed by a Library of 2,9-Diazaperopyrenium Dications

et al. 2015

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“…For example, N , N ′-bis(isooctyl)-PDIs show very poor solubility in common organic solvents (solubility less than 1 mg/mL in CH 2 Cl 2 ). For another example, Deyama et al investigated the solubility of several kinds of PDIs containing perfluoroalkyl groups and found cis - N , N ′-bis[2-(1 H ,1 H -perfluoroheptyl)phenyl]-PDIs have the maximum solubility of 14 mg/mL in chloroform . In a review, Langhals summarized the solubility of PDIs with two unbranched alkyl groups attached to nitrogen atoms and concluded that the solubility of those compounds is lower than 0.1 mg/mL in CHCl 3 .…”

Section: Resultsmentioning

confidence: 99%

Core-Perfluoroalkylated Perylene Diimides and Naphthalene Diimides: Versatile Synthesis, Solubility, Electrochemistry, and Optical Properties

Yuan

Xiao

et al. 2010

J. Org. Chem.

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By a strategy featuring perfluoroalkylation of the highly soluble intermediates and their further efficient transformations to target compounds, a versatile synthesis of core-perfluoroalkylated perylene diimides (PDIs) and naphthalene diimides (NDIs) was developed, and PDIs perfluoroalkylated at 1-position or 1,6-positions and core-perfluoroalkylated NDIs were first obtained. By esterification, perfluoroalkylation, hydrolysis, and condensation with amine, 1-perfluorooctyl-PDIs (7b, 7c, and 7e), 1,7-bis(perfluorooctyl)-PDIs (8a-c and 8e-g), 1,6-bis(perfluorooctyl)-PDIs (8'e), a mixture of 1,7-bis(trifluoromethyl)-PDIs and 1,6-bis(trifluoromethyl)-PDIs (11b and 11'b, 11d and 11'd, in a ratio of 19:1), 2-perfluorooctyl-NDIs (20a-d), and 2,6-bis(perfluorooctyl)-NDIs (21a-21d) were efficiently synthesized. Five valuable intermediates--1-perfluorooctylperylene dianhydride (5), 1,7-bis(perfluorooctyl)perylene dianhydride (6) 1,6-bis(perfluorooctyl)perylene dianhydride (6'), 2-perfluorooctylnaphthalene dianhydride (18), and 2,6-bis(perfluorooctyl) naphthalene dianhydride (19)--were also obtained, and they can condense with many amines to produce PDIs containing different functional side chains on the imide nitrogen atoms. Solubility, electrochemistry, and optical properties of the above core-perfluoroalkylated PDIs and NDIs were investigated. Core-perfluoroalkylated 8e, 8f, 8'e, mixture of 11d and 11'd, 20b, and 20d with excellent solubility in common organic solvents are competitive as candidates as solution processable semiconductors. Core-perfluoroalkylated PDIs and NDIs with experimental LUMO energy of 4.04-4.34 eV demonstrate strong electron accepting ability. For core-perfluoroalkylated PDIs, the maximum absorptions display blue shifts of 6-18 nm and the maximum molar extinction coefficients decrease obviously relative to those of unsubstituted PDIs, and they inherit the strong fluorescence from the PDIs family, which makes them promising fluorescent dyes.

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“…1͑a͔͒. 15 The absence of core substituents makes the torsion of the PTCDI system very small, and allows a very dense molecular packing, which leads to high charge carrier mobilities.…”

mentioning

confidence: 99%

Air-stable n-channel organic thin-film transistors with high field-effect mobility based on N,N′-bis(heptafluorobutyl)-3,4:9,10-perylene diimide

Liu

Bao

et al. 2007

Applied Physics Letters

150

156

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The thin-film transistor characteristics of n-channel organic semiconductor, N,N′-bis(2,2,3,3,4,4,4-heptafluorobutyl)-perylene tetracarboxylic diimide, are described. The slip-stacked face-to-face molecular packing allows a very dense parallel arrangement of the molecules, leading to field-effect mobility as high as 0.72cm2V−1s−1. The mobility only slightly decreased after exposure to air and remained stable for more than 50days. Our results reveal that molecular packing effects such as close stacking of perylene diimide units and segregation effects imparted by the fluorinated side chains are crucial for the air stability.

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3,4,9,10-Perylenetetracarboxdiimides containing perfluoroalkyl substituents

Cited by 14 publications

References 14 publications

Anticancer Activity Expressed by a Library of 2,9-Diazaperopyrenium Dications

Anticancer Activity Expressed by a Library of 2,9-Diazaperopyrenium Dications

Core-Perfluoroalkylated Perylene Diimides and Naphthalene Diimides: Versatile Synthesis, Solubility, Electrochemistry, and Optical Properties

Air-stable n-channel organic thin-film transistors with high field-effect mobility based on N,N′-bis(heptafluorobutyl)-3,4:9,10-perylene diimide

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