Dual Association Modes of the 2,5,8‐Tris(pentafluorophenyl)phenalenyl Radical

Uchida, Kenzo; Hirao, Yasukazu; Kurata, Hiroyuki; Kubo, Takashi; Hatano, Sayaka; Inoue, Katsuya

doi:10.1002/asia.201402187

Cited by 67 publications

(45 citation statements)

References 39 publications

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“…The X ray crystallographic analysis of the crystal showed that 5 adapts a σ dimer form (5 2 ) in the solid state (Figure 5a). 25 The 1 H NMR spectrum of the colorless crystals in CDCl 3 showed six sharp singlet signals in the temperature range 233 298 K, consistent with the σ dimer form. No peak originating from a π dimer form was observed.…”

Section: Challenge To Ideal One Dimensional (1d) Stack Of Phenalenyl mentioning

confidence: 96%

Recent Advances in the Chemistry of Phenalenyl

Uchida¹,

Kubo

2016

J. Synth. Org. Chem. Jpn.

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Phenalenyl radical is an odd alternant hydrocarbon radical with a highly symmetric (D 3h ) structure. The high stability and amphoteric redox nature of this radical have triggered studies on its chemical reactivity, physical properties, and functionalities. The main problem hindering the use of phenalenyl radicals as the molecular components of functional materials is their propensity to σ dimerization. Challenging issue will lie in understanding the self association character and also in controlling the molecular overlap motif. This article summarizes our studies on the self association behavior of phenalenyl radicals.

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Section: Challenge To Ideal One Dimensional (1d) Stack Of Phenalenyl mentioning

confidence: 96%

Recent Advances in the Chemistry of Phenalenyl

Uchida¹,

Kubo

2016

J. Synth. Org. Chem. Jpn.

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“…In recent years, a plethora of functional molecular materials based on PLY and its derivatives have been realized, displaying diverse fascinating optical, conducting, and magnetic properties. 1,[18][19][20][21]41,42 We note that the new molecular species introduced in this work may be equally exploited as building blocks of new functional materials for the realization of unique material properties. The double π−π bonding in fact consists of two separate single "bonds" of comparable strength as the single π−π-bonded PLY dimer.…”

Section: The Journal Of Physical Chemistry Lettersmentioning

confidence: 99%

Pancake π–π Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls

Tian

Sumpter

et al. 2015

J. Phys. Chem. Lett.

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Chemical bonding interactions are the main driving force for the formation of molecules and materials from atoms. The two-electron/multicenter pancake π-π bonding found in phenalenyl (PLY, 1) radical π-dimers is intriguing due to its unconventional nature of covalent bonding for molecular aggregations and its propensity to induce unique optical, electronic, and magnetic properties. By using high-level quantum chemistry calculations, we show that the B- or N-doped PLYs (2 and 4), usually considered closed-shell and therefore trifling, can be rendered open-shell singlet by proper edge substitutions (3 and 5). The resulting two unpaired valence electrons on each molecular unit contribute to the formation of a genuine pancake-shaped 4e/all-sites double π-π bonding upon intermolecular π-dimerization, in contrast to the 2e/half-sites single π-π bonding in the parent PLY π-dimers. The unusual double π-π bonding motif discovered in these PLY analogues may broaden the landscape of, and find new applications for, intermolecular covalent bonding interactions.

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“…[15][16][17] In a few cases, 1D π-stacking columns are formed with large intermolecular separations of~3.78 (ref. 13) and 3.65 Å, 19 due to bulky protection groups, the latter of which shows a band around 800 nm. 19 π-Stacked structures of π-conjugated PNL dimers (1/2 unpaired electron per PNL unit) [20][21][22] and those of singlet-diradical bisphenalenyls 23 (one unpaired electron per PNL unit) exhibit NIR absorption bands.…”

mentioning

confidence: 99%

“…13) and 3.65 Å, 19 due to bulky protection groups, the latter of which shows a band around 800 nm. 19 π-Stacked structures of π-conjugated PNL dimers (1/2 unpaired electron per PNL unit) [20][21][22] and those of singlet-diradical bisphenalenyls 23 (one unpaired electron per PNL unit) exhibit NIR absorption bands. Bis(dithiazolyl) radicals 24,25 form 1D π-stacks with intercolumnar S•••S and S•••N contacts, showing lowenergy absorption bands around~2500 nm (~0.5 eV).…”

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confidence: 99%

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Near-infrared absorption of π-stacking columns composed of trioxotriangulene neutral radicals

et al. 2017

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A long-wavelength photoabsorption of organic molecules has been noticed because of the potential as materials. In addition to the extension of π conjugation, molecular aggregation has been utilized to realize the elongation of absorption wavelength. We report strong near-infrared absorptions of trioxotriangulene neutral radicals in the crystalline state and large-scale theoretical calculations of the radical assemblies interpreting the mechanism of optical properties. Polarized absorption spectra and X-ray diffraction of the crystals clarified that an unusual π-stacking column consisting of π-dimers is key for this absorption. Quantum chemical calculations based on time-dependent density functional theory revealed that the π-dimer shows an electronic transition between frontier orbitals generated by strong coupling of the delocalized singly occupied orbitals of monomers. The interdimer interaction of transition dipole moments, which are parallel to the column, elucidated the increase of absorption wavelength. The divide-andconquer Green function method enabled the large-scale time-dependent density functional theory calculation up to a 60mer, where the maximum number of atoms is 4380, reproducing the near-infrared absorptions of trioxotriangulene crystals. The present method to investigate the mechanism of the long-wavelength photoabsorption is useful for developing organic materials consisting of stable neutral radicals.

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Dual Association Modes of the 2,5,8‐Tris(pentafluorophenyl)phenalenyl Radical

Cited by 67 publications

References 39 publications

Recent Advances in the Chemistry of Phenalenyl

Recent Advances in the Chemistry of Phenalenyl

Pancake π–π Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls

Near-infrared absorption of π-stacking columns composed of trioxotriangulene neutral radicals

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