Beyond Perylene Diimides—Diazaperopyrenium Dications as Chameleonic Nanoscale Building Blocks

Basuray, Ashish N.; Rouville, Henri Pierre Jacquot De; Hartlieb, Karel J.; Fahrenbach, Albert C.

doi:10.1002/asia.201200780

Cited by 11 publications

(3 citation statements)

References 64 publications

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“…Recently, we have demonstrated the ability of dicationic diazaperopyrenium (DAPP 2+ ) units (Scheme ), which have an extended, electron-rich aromatic core region flanked on either side by electron-deficient pyridinium rings, to perform both homophilic recognition , involving the interaction of structurally and electronically similar, if not identical, species (e.g., pimerization of viologens)and heterophilic recognition , consisting of constitutionally different species (e.g., donor–acceptor interactions)in a single redox state. While the homophilic recognition of DAPP 2+ units, compensating the Coulombic repulsion through strong π–π interactions between the large aromatic core at the center of DAPP 2+ , has been found in their solid-state superstructures, most of the current work focuses on the heterophilic recognition of DAPP 2+ units in MIMs, graphene exfoliation applications, host–guest inclusion complexes, and anticancer activity .…”

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Toward a Charged Homo[2]catenane Employing Diazaperopyrenium Homophilic Recognition

Gong¹,

Zhou²,

Hartlieb³

et al. 2018

J. Am. Chem. Soc.

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An octacationic diazaperopyrenium (DAPP)-based homo[2]catenane (DAPPHC), wherein no fewer than eight positive charges are associated within a mechanically interlocked molecule, has been produced in 30% yield under ambient conditions as a result of favorable homophilic interactions, reflecting a delicate balance between strong π-π interactions and the destabilizing penalty arising from Coulombic repulsions between DAPP units. This DAPPHC catenane is composed of two identical mechanically interlocked tetracationic cyclophanes, namely DAPPBox, each of which contains one DAPP unit and one extended viologen (ExBIPY) unit, linked together by two p-xylylene bridges. The solid-state structure of the homo[2]catenane demonstrates how homophilic interactions play an important role in the formation of DAPPHC, in which the mean ring planes of the two DAPPBox cyclophanes are oriented at about 60° with respect to each other, with a centroid-to-centroid separation of 3.7 Å between the mean planes of the outer ExBIPY and inner DAPP units, and 3.6 Å between the mean planes of the two inner DAPP units. We show that irradiation of the DAPPHC catenane at 330 nm in acetonitrile solution results in simultaneous energy and electron transfer. The latter occurs from the inner DAPP dimer to the outer ExBIPY unit, leading to the generation of a temporary charge-separated state within a rigid and robust homo[2]catenane. Compared to DAPPBox, both forward- and back-electron transfer in DAPPHC occur with faster rates, owing to the closer proximity between the electron donor and acceptor in the homo[2]catenane than in the separated cyclophane.

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Toward a Charged Homo[2]catenane Employing Diazaperopyrenium Homophilic Recognition

Gong¹,

Zhou²,

Hartlieb³

et al. 2018

J. Am. Chem. Soc.

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“…Recently, we have been investigating − the materials properties of the N , N ′-dimethyl-2,9-diazaperopyrenium dication (dimethyl-DAPP 2+ ), which has (Figure ) an extended, electron-rich aromatic core region flanked on either side by electron-deficient pyridinium rings. This compound has found use in mechanically interlocked molecules (MIMs), graphene exfoliation applications, and in host–guest inclusion complexes. , The aqueous solubility, imparted by the dicationic nature of this compound, led us to consider whether the extended aromatic region present in dimethyl-DAPP 2+ and related compounds could prove useful in identifying cancer therapeutic agents.…”

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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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The Fundamentals of Making Mechanical Bonds

2016

The Nature of the Mechanical Bond

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Beyond Perylene Diimides—Diazaperopyrenium Dications as Chameleonic Nanoscale Building Blocks

Abstract: Cast peryl before swine: A new field of chemistry has emerged by using a unique, and highly processable class of functionalized perylene‐based molecules, namely, diazaperopyrenium dications, thereby expanding the existing library of malleable graphene‐mimetic compounds.

Cited by 11 publications

References 64 publications

Toward a Charged Homo[2]catenane Employing Diazaperopyrenium Homophilic Recognition

Toward a Charged Homo[2]catenane Employing Diazaperopyrenium Homophilic Recognition

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

The Fundamentals of Making Mechanical Bonds

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