Isolation of Tetracyano‐Naphthalenediimide and Its Stable Planar Radical Anion

Kumar, Yogendra; Kumar, Sharvan; Mandal, Kalyanashis; Mukhopadhyay, Pritam

doi:10.1002/anie.201807836

Cited by 74 publications

(45 citation statements)

References 52 publications

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“…[2] In fact, the intrinsic high reactivity of radical species and their susceptibility to reoxidation by air is ubiquitous.O ne of the most notable strategies for accessing these systems is to use extremely electron-deficient p-systems as precursors,t hus endowing the final product with higher electron affinity for spontaneously capturing electrons to form stable organic radicals. [3] Ag rowing number of highly electron-deficient precursors with lower LUMO levels were reported. [4] However,t he rational design of as ystem in which the electron deficiencya nd stability are balanced, allowing the construction of at wo-state (neutral and reduced) stable electronaccepting material, remains very challenging.…”

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confidence: 99%

Fulvalene‐Embedded Perylene Diimide and Its Stable Radical Anion

Zhang,

Jiang,

Wang

2019

Angew Chem Int Ed

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The first example of a two‐state (neutral and reduced), stable electron‐accepting material and its radical anion is presented. FV‐PDI, generated from cyclocarbonylation and then a carbonyl coupling reaction, shows a largely degenerate LUMO of −4.38 eV based on the delocalization of π‐electrons across the whole molecular skeleton through a fulvalene bridge. The stability and electron affinity allow spontaneous electron transfer to afford a stable radical anion. Spectroscopic characterization and structural elucidation showed that the radical anion [FV‐PDI].− has remarkable stability and near‐infrared absorptions extending to 1200 nm. Single‐crystal X‐ray diffraction analyses revealed significant changes in the molecular shape and packing arrangement of the formed radical anion. The central C−C bond linking the two PDI halves is lengthened from approximately 1.33 to 1.43 Å, and the alternating arrangement of positively and negatively charged units favor the stable charge‐transfer complex.

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confidence: 99%

Fulvalene‐Embedded Perylene Diimide and Its Stable Radical Anion

Zhang,

Jiang,

Wang

2019

Angew Chem Int Ed

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“…Cyclic voltammetry was performed to investigate the redox properties of OT‐1 and OT‐2 in a 1.0 m m solution of tetrabutylammonium hexafluorophosphate (TBAPF 6 ) in dichloromethane (Figure ). Both OT‐1 and OT‐2 showed double reversible reduction waves in the tested electrochemical window, representing the first reduction of the NMI unit to NMI radical anion followed by formation of diradical anions localised on each acceptor groups . The first reduction potential shifted to lower values on going from OT‐1 ( E red1 =−1.10) to OT‐2 ( E red1 =−0.96), the and the first oxidation potentials were 1.43 and 1.67 eV, respectively.…”

Section: Resultsmentioning

confidence: 97%

Supramolecular Nanowires from an Acceptor–Donor–Acceptor Conjugated Chromophore

Chakraborty¹,

Varghese

Ghosh

2019

Chemistry A European J

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Oligothiophened erivatives have been extensively studied as p-type semiconducting materials in organic electronics applications. This work reports the synthesis, self-assembly and photophysical properties of acceptor-donor-acceptor (A-D-A)-type oligothiophene derivatives by endgroup engineering of quaterthiophene (QT) with naphthalene monoimide (NMI) chromophores that are further connected to at rialkoxy benzamide wedge. Conjugation to the NMI units reduces the HOMO-LUMO gap significantly,a nd consequently the absorption spectrum exhibits ab athochromic shift of about 50 nm compared with QT.F urthermore, extended H-bonding interactions among the amido groups of the peripheral wedges produce entangled fibrillar nanostructures and gelation in hydrocarbon solvents such as methylcyclohexane, wherein the A-D-Achromophore exhibits typicalH -aggregation. On the contrary,t he fact that the same chromophore, lacking only the amido units, does not produce gels or H-aggregates indicates strong impact of Hbondingo nt he self-assembly.C omputational studies revealed the electronic properties of the chromophorea nd predicted the geometry of ad imer in the H-aggregate that reasonably matches with the experimental results. Bulk electrical conductivitym easurements determined an excellent conductivity of 2.3 10 À2 Scm À1 for the H-aggregated system (OT-1), which is two orders of magnitude highert han that of the same chromophore lacking the amido groups (OT-2).Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

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“…NDIs have functioned as anion‐π [5, 26–28] catalysts, [25] ion channels, [28, 29] sensors, [29] artificial photosystems, [6, 8, 30] semi‐conductors, [6, 31] G‐quartet stabilizers, [32] and self‐assembled matter in all variations, such as vesicles, [33] nanotubes, [34] mono‐ and multilayers on surfaces, [8, 30, 33] dynamic covalent libraries, knotted molecular topologies or donor‐acceptor stacks [33–36] . COC‐NDIs will be of interest to explore within this existing functional space, particularly with regard to artificial photosystems [8] .…”

Section: Figurementioning

confidence: 99%

Naphthalenediimides with Cyclic Oligochalcogenides in Their Core

Shybeka

Aster

Cheng

et al. 2020

Chemistry A European J

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Naphthalenediimides (NDIs) are privileged scaffolds par excellence, of use in functional systems from catalysts to ion channels, photosystems, sensors, ordered matter in all forms, tubes, knots, stacks, sheets, vesicles, and colored over the full visible range. Despite this extensively explored chemical space, there is still room to discover core‐substituted NDIs with fundamentally new properties: NDIs with cyclic trisulfides (i.e., trisulfanes) in their core absorb at 668 nm, emit at 801 nm, and contract into disulfides (i.e., dithietes) upon irradiation at <475 nm. Intramolecular 1,5‐chalcogen bonds account for record redshifts with trisulfides, ring‐tension mediated chalcogen‐bond‐mediated cleavage for blueshifts to 492 nm upon ring contraction. Cyclic oligochalcogenides (COCs) in the NDI core open faster than strained dithiolanes as in asparagusic acid and are much better retained on thiol exchange affinity columns. This makes COC‐NDIs attractive not only within the existing multifunctionality, particularly artificial photosystems, but also for thiol‐mediated cellular uptake.

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Isolation of Tetracyano‐Naphthalenediimide and Its Stable Planar Radical Anion

Cited by 74 publications

References 52 publications

Fulvalene‐Embedded Perylene Diimide and Its Stable Radical Anion

Fulvalene‐Embedded Perylene Diimide and Its Stable Radical Anion

Supramolecular Nanowires from an Acceptor–Donor–Acceptor Conjugated Chromophore

Naphthalenediimides with Cyclic Oligochalcogenides in Their Core

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