Modulating the properties of buckybowls containing multiple heteroatoms

Zhu, Guanxing; Song, Yujun; Zhang, Qianyu; Ding, Weiwei; Chen, Xinxin; Wang, Yuannan; Zhang, Gang

doi:10.1039/d0qo01452d

Cited by 33 publications

(19 citation statements)

References 70 publications

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“…Having assessed that 3 can undergo two-electron oxidation in the presence of AgSbF 6 and that the resulting dication 4 is indeed an aromatic fully benzenoid species ( Figure 2 b), oxidation was then carried out by treating 3 with 2 equiv of oxidant in dry degassed 1,2-dichloroethane (DCE), resulting in a deep blue solution. As reported for similar systems, 13 the purification procedure consisted of filtration to remove silver and the precipitation from petroleum ether (PE) to get rid of unreacted materials, affording 4 in a high 85% yield as a clean product. Interestingly, decreasing the amount of oxidants employed only resulted in mixtures of 3 and 4 , preventing the observation and isolation of the radical cation intermediate.…”

Section: Results and Discussionmentioning

confidence: 99%

“… 8 − 12 Moreover, the possibility of introducing the heteroatoms in a neutral state and oxidizing them in a later step can result in materials with a behavior depending on the oxidation state and in molecular switching capabilities due to hybridization change. 13 , 14 While various examples of PAHs presenting a single charged atom in their structure have been reported in different contributions, 2 , 7 , 8 , 15 , 16 doubly charged ones are less explored, with notable examples presenting O, N, S, or combinations of these heteroatoms, using both surface and solution-based chemistry. 17 − 26 From this point of view, parent and π-extended dihydrophenazines represent valuable precursors toward the generation of 2 + N-doped PAHs.…”

Section: Introductionmentioning

confidence: 99%

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Phenanthrene-Extended Phenazine Dication: An Electrochromic Conformational Switch Presenting Dual Reactivity

et al. 2022

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The synthesis and isolation of one of the few examples of a π-extended diamagnetic phenazine dication have been achieved by oxidizing a phenanthrene-based dihydrophenazine precursor. The resulting dication was isolated and fully characterized, highlighting an aromatic distorted structure, generated by the conformational change upon the oxidation of the dihydrophenazine precursor, which is also correlated with a marked electrochromic change in the UV–vis spectrum. The aromaticity of the dication has also been investigated theoretically, proving that the species is aromatic based on all major criteria (structural, magnetic, and energetic). Moreover, the material presents an intriguing dual reactivity, resulting in ring contraction to a π-extended triarylimidazolinium and reduction to the dihydrophenazine precursor, depending on the nature of the nucleophile involved. This result helps shed light on the yet largely unexplored reactivity and properties of extended dicationic polycyclic aromatic hydrocarbons (PAHs). In particular, the fact that the molecule can undergo a reversible change in conformation upon oxidation and reduction opens potential applications for this class of derivatives as molecular switches and actuators.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Phenanthrene-Extended Phenazine Dication: An Electrochromic Conformational Switch Presenting Dual Reactivity

et al. 2022

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“…In 2021, Zhang et al described the synthesis of the thiazine-fused buckybowl 55.3 and its derivatives ( Scheme 55 ). 92 The synthesis began with the copper(I)-catalyzed cyclodimerization of the dibromophenothiazine 55.1 . The same transformation under Buchwald–Hartwig conditions only led to a complex product mixture.…”

Section: Perylenoidsmentioning

confidence: 99%

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

et al. 2021

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“…Notably, seminal works on the pyrrole-embedded curved PAHs were independently reported by Nozaki and Shinokubo. 18,19 Consecutively, Wang and co-workers demonstrated acridone (6,7) [20][21][22] and phenothiazine (8) 23 containing PAHs, as suitable building blocks to ensure the desired curvature for the construction of concave and boat-like conformations, respectively. Recently, the research group of Gryko showed the utility of pyrrolo [3,2-b]pyrrole in forming a bucky-bowl like system, with inverse Stone-Thrower-Wales defects, first through "on surface" 24 and subsequently "in solution" 25 approaches (Figure 1b, 9).…”

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confidence: 99%

TADF/RTP OLED organic emitters based on concaved N-PAHs with tunable intrinsic D-A electronic structure

Wagner

Crocomo

Kochman³

et al. 2022

Preprint

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The introduction of pyrrolic nitrogen dopants into the central sites of polycyclic aromatic hydrocarbons (PAHs) often gives rise to characteristic bowl-shaped structures due to the simultaneous introduction of 5- and/or 7-membered cycles. Although the incorporation of these heteroatoms achieves excellent electron-donating ability, the application of this strat-egy for the design of optoelectronics is hampered by typically low photoluminescence quantum yields (PLQYs). In order to address this issue, in the present study we report the synthesis and characterization of the first curved and fully conju-gated nitrogen-doped PAHs in which an electronically diverse phenazine terminus serves as the electron-accepting moie-ty. We show that the curvature of the molecular skeleton increases the spatial separation between the HOMO and the LUMO, leading to low singlet-triplet gaps, which are essential for high reverse intersystem crossing (RISC) rates. Moreo-ver, we evaluate the utility of the concave N-doped systems as TADF/RTP emitters, which has not been explored so far in the context of non-planar N-PAHs. By varying the electron-accepting ability of the phenazine terminus, we are able to tune the PLQY of the given compounds in a range from 9% to 86% (for a dinitrile substituted derivative). As a proof of con-cept, we constructed solid-state OLED devices exhibiting yellow to orange emission. The best-performing compound, built from a 3-(trifluoromethyl)phenyl decorated phenazine acceptor, shows a maximum external EL quantum efficiency (EQE) of 12%, which is the highest EQE in an curved D-A embedded N-PAH to date

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Modulating the properties of buckybowls containing multiple heteroatoms

Abstract: Nitrogen-centered buckybowls with sulfur decoration at the rim were synthesized and characterized. The buckybowls demonstrate tunable properties depending on the state of the sulfur atom.

Cited by 33 publications

References 70 publications

Phenanthrene-Extended Phenazine Dication: An Electrochromic Conformational Switch Presenting Dual Reactivity

Phenanthrene-Extended Phenazine Dication: An Electrochromic Conformational Switch Presenting Dual Reactivity

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

TADF/RTP OLED organic emitters based on concaved N-PAHs with tunable intrinsic D-A electronic structure

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