Trioxotriangulene with carbazole: a donor–acceptor molecule showing strong near-infrared absorption exceeding 1000 nm

Murata, Tsuyoshi; Kariyazono, Kazuki; Ukai, Shusaku; Ueda, Akira; Kanzaki, Yuki; Shiomi, Daisuke; Sato, Kazunobu; Takui, Takeji

doi:10.1039/c9qo00663j

Cited by 9 publications

(10 citation statements)

References 79 publications

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“…Molecules composed of an electron donor (D) and an electron acceptor (A) are other candidates for small Δ E H–L values, − although D–A molecules with an absorption band exceeding λ max = 1000 nm are rare. − Because the HOMO and LUMO of the D–A molecules are predominantly formed by bonding and antibonding interactions of the donor-HOMO and the acceptor-LUMO, respectively, the Δ E H–L values of D–A molecules are mainly determined by two factors: (1) the energy difference between the donor-HOMO and the acceptor-LUMO (Δ E D–A ), and (2) the strength of the interaction between them ( E Int ). When Δ E D–A is significantly large, regardless of the strength of E Int , Δ E H–L becomes large (Figure a: strong E Int , Figure b: weak E Int ).…”

Section: Introductionmentioning

confidence: 99%

HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

et al. 2020

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π-Conjugated molecules with small highest occupied molecular orbital (HOMO)−lowest unoccupied molecular orbital (LUMO) energy gaps (ΔE H−L ) have been extensively studied because of their unique optoelectronic properties. Although the expansion of πconjugation is one of the well-known approaches for designing molecules with small ΔE H−L values, such an approach inevitably gives large πconjugated molecules sometimes suffering from synthetic difficulty and low solubility toward organic solvents. To develop relatively small donor− acceptor molecules with small ΔE H−L values, we have designed and synthesized π-conjugated zwitterions composed of electron-donating anions, such as phenoxide and anthroxide, and electron-accepting cations, such as pyridinium and acridinium. The energy difference between the HOMO of the anion and the LUMO of the cation (ΔE D−A ) and the interplanar angle between them (φ DA ) have a crucial effect on ΔE H−L , and hence, on the electronic structures and optoelectronic properties of these zwitterions. The zwitterions with small ΔE D−A and large φ DA have a small ΔE H−L of ca. 1 eV and show amphoteric redox properties and near-infrared (NIR) electronic absorption exceeding λ = 1000 nm. The NIR absorption responds to solvent polarity, temperature, and acid addition. This molecular design will generate small π-conjugated donor−acceptor molecules with small ΔE H−L values.

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Section: Introductionmentioning

confidence: 99%

HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

et al. 2020

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“…Trioxotriangulene ( TOT 1 , Scheme 1 ) is a fused-polycyclic hydrocarbon [ 39 , 40 ] functionalized with three oxo-groups, and its neutral radical is highly stable even without steric protections due to the delocalization of electronic-spin [ 41 ]. Our recent investigation revealed various intriguing physical properties and functions of TOT derivatives based on the redox activity and self-assembling ability by π-stacking [ 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 ]. We also demonstrated that TOT exhibits a four-stage redox ability from neutral radical to radical tetraanion species.…”

Section: Introductionmentioning

confidence: 99%

2D Coordination Network of Trioxotriangulene with Multiple Redox Abilities and Its Rechargeable Battery Performance

Murata

Koide

Nobukuni

et al. 2020

IJMS

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A three-fold symmetric trioxotriangulene derivative with three pyridyl groups as coordinating sites was designed and synthesized. In a cyclic voltammetry measurement, the trioxotriangulene skeleton exhibited a multi-stage redox ability from neutral radical to radical tetra-anion species. In the zinc complex of monoanion species, three pyridyl groups coordinated to the zinc ion to build up a two-dimensional coordination network with a cavity larger than 12 Å in diameter. This complex was utilized as a cathode active material of a lithium ion battery, and it exhibited a capacity of ca. 60 mAh g−1 per the weight of the active material with a stable cycling performance up to 1000 cycles. This work shows that the coordination network formed by the trioxotriangulene-based ligand was effective in the improvement of cycle performance of the organic rechargeable battery.

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“…We recently succeeded in the synthesis and isolation of 4,8,12-trioxotriangulene ( TOT , 1 ) and its derivatives 23,28−34 as a new class of polycyclic carbon-centered organic neutral π-radicals with high air stability (Figure 1a). 35 TOT neutral radicals are treatable under an ambient condition in both solid and solution states even without steric protection groups, and no decomposition was found until 350 °C.…”

Section: Introductionmentioning

confidence: 99%

“…We recently succeeded in the synthesis and isolation of 4,8,12-trioxotriangulene ( TOT , 1 ) and its derivatives ,− as a new class of polycyclic carbon-centered organic neutral π-radicals with high air stability (Figure a) .…”

Section: Introductionmentioning

confidence: 99%

Air-Stable Thin Films with High and Anisotropic Electrical Conductivities Composed of a Carbon-Centered Neutral π-Radical

et al. 2019

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Air-stable thin films (50–720 nm thickness) composed of a carbon-centered neutral π-radical with high and anisotropic electrical conductivities were fabricated by vapor deposition of 4,8,12-trioxotriangulene (TOT). The thin films were air-stable over 15 months and were the aggregate of TOT microcrystals, in which a one-dimensional π-stacking column was formed through the strong singly occupied molecular orbital (SOMO)–SOMO interaction with two-electron-multicenter bond among the spin-delocalized π-planes. The orientations of the one-dimensional column of TOT were changed depending on the deposition rate and substrates, where face-on-oriented thin films were epitaxially grown on the graphite 0001 surface, and edge-on-oriented thin films were grown on glass, SiO2, and indium tin oxide substrates under a high-deposition rate condition. The films showed high electrical conductivities of 2.5 × 10–2 and 5.9 × 10–5 S cm–1 along and perpendicular to the π-stacking column, respectively, for an edge-on oriented thin film.

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Trioxotriangulene with carbazole: a donor–acceptor molecule showing strong near-infrared absorption exceeding 1000 nm

Abstract: A donor–acceptor type trioxotriangulene neutral radical derivative having three carbazolyl groups as electron-donors was newly synthesized, and exhibited a strong near-infrared photo absorption over 1000 nm.

Cited by 9 publications

References 79 publications

HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

2D Coordination Network of Trioxotriangulene with Multiple Redox Abilities and Its Rechargeable Battery Performance

Air-Stable Thin Films with High and Anisotropic Electrical Conductivities Composed of a Carbon-Centered Neutral π-Radical

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