Complexation of B(C6F5)3 and 9,10-Dicyanoanthracene: Dual Role of Borane as Spatial and Electronic Tuner

Imagawa, Taiki; Nakamoto, Masaaki; Shang, Rong; Adachi, Yoshinori; Ohshita, Joji; Tsunoji, Nao; Yamamoto, Yohsuke

doi:10.1246/cl.200339

Cited by 7 publications

(7 citation statements)

References 35 publications

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“…To gain further insight into the electronic structures, UV/vis measurements of 2 and 3 in THF solution were performed (Figure 2). The absorption spectrum of 2 lost the vibronic structure observed in the spectrum of neutral species 1 [28] . The absorption maximum at 377 nm was over 100 nm, hypsochromically shifted from that of 1 at 489 nm, suggesting a quinoidal structure in solution, which is consistent with the 13 C NMR results.…”

Section: Resultssupporting

confidence: 84%

“…The 11 B and 19 F NMR spectra of 2 showed clean and sharp signals in solution at ambient temperature, indicating that the boranes did not dissociate in THF and that no BCF‐THF complex was formed. This strong coordination of BCF upon reduction is in stark contrast to the neutral Lewis adduct 1 , which dissociates in a Lewis basic solvent (THF) to yield coordination‐free 9,10‐dicyanoanthracene, DCA, and THF‐BCF [28] . Overall, the other dianionic compounds, 2 CIP and 2 PI , showed similar trends.…”

Section: Resultsmentioning

confidence: 86%

“…In this study, we investigated the effect of Lewis adduct formation in antiaromatic systems using the reduction of a Lewis complex consisting of 9,10‐dicyanoanthracene (DCA) and tris(pentafluorophenyl)borane, [28] as a probe (Figure 1b). The changes in the electronic structure both experimentally and computationally, and a decrease in antiaromaticity upon Lewis adduct formation have been found.…”

Section: Introductionmentioning

confidence: 99%

“…Although several examples of antiaromaticity quenching on borole derivatives via π-conjugation interruption of Lewis adduct formation at the boron center have been reported, [21][22][23][24][25] only two examples of the effect of Lewis adduct formation on remote antiaromatic systems have been reported. [26,27] In this study, we investigated the effect of Lewis adduct formation in antiaromatic systems using the reduction of a Lewis complex consisting of 9,10-dicyanoanthracene (DCA) and tris(pentafluorophenyl)borane, [28] as a probe (Figure 1b). The changes in the electronic structure both experimentally and computationally, and a decrease in antiaromaticity upon Lewis adduct formation have been found.…”

Section: Introductionmentioning

confidence: 99%

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Complexation‐Triggered Fluctuation of π‐Conjugation on an Antiaromatic Dicyanoanthracene Dianion

Imagawa,

Okazawa,

Yoshizawa

et al. 2023

Chemistry A European J

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The formation of Lewis pairs is an important chemical concept. Recently, the complexation of Lewis acidic tris(pentafluorophenyl)borane with Lewis basic moieties and subsequent reduction has emerged as a fascinating strategy for designing novel reactions and structures. The impact of the complexation and subsequent reduction of antiaromatic systems bearing Lewis base moieties has been investigated. We found how Lewis adduct formation stabilizes an antiaromatic system consisting of 9,10‐dicyanoanthracene and tris(pentafluorophenyl)borane by using synthesis, X‐ray crystallography, spectroscopic analysis, and quantum chemical calculations.

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Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Complexation‐Triggered Fluctuation of π‐Conjugation on an Antiaromatic Dicyanoanthracene Dianion

Imagawa,

Okazawa,

Yoshizawa

et al. 2023

Chemistry A European J

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“…Moreover, the fluorescence quantum yields of 13 were enhanced in both solution (Φ s = 0.86 vs. 0.99) and solid state (Φ f = 0.21 vs. 0.50) upon B←N coordination. [ 50 ] B←N complexation was also observed between the alkynyl aryl‐conjugated imine (14) and various B Lewis acids, e.g., BX 3 (X = F, Cl, and Br), BCF, and BPh 3 to shifted the absorption and fluorescence to lower energy. [ 51 ] Besides solid fluorescence, the crystallization fluorescence enhancement was also surveyed in the crystal of 15‐BCF complex.…”

Section: Intermolecular B←n Coordinationmentioning

confidence: 99%

B←N Coordination: From Chemistry to Organic Photovoltaic Materials

Huang

Wang

Xiang

et al. 2021

Adv Energy and Sustain Res

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Coordination between boron Lewis acid and nitrogen Lewis base (B←N) is a classically chemical issue that has been known for several decades. Recently, this B←N chemistry developed into a new stage toward electronic materials, e.g., adjusting optoelectronic properties of N‐based conjugated molecules via adding B Lewis acids, synthesizing B←N‐bridged conjugated units, and further constructing B←N‐embedded organic photovoltaic (OPV) materials. Herein, these progresses are systematically summarized starting from certain chemical issues concerning B←N coordination, e.g., Lewis acidity of typical B Lewis acids and their interactions with N‐contained conjugated molecules. Then, some fused and ladder‐type B←N‐bridged units are reviewed in terms of the relationship between molecular structures and optoelectronic properties. Finally, the recently flourished B←N‐embedded OPV materials are summarized. The prospect of OPV materials concerning B←N coordination is also proposed, hoping to attract more attention to this filed and motivate its rolling rapidly.

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Homolytic C−H Bond Activation by Phosphine−Quinone‐Based Radical Ion Pairs

Helling,

van der Zee,

Hofman

et al. 2023

Angewandte Chemie

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Herein, we present the formation of transient radical ion pairs (RIPs) by single‐electron transfer (SET) in phosphine−quinone systems and explore their potential for the activation of C−H bonds. PMes3 (Mes=2,4,6‐Me3C6H2) reacts with DDQ (2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone) with formation of the P−O bonded zwitterionic adduct Mes3P−DDQ (1), while the reaction with the sterically more crowded PTip3 (Tip=2,4,6‐iPr3C6H2) afforded C−H bond activation product Tip2P(H)(2‐[CMe2(DDQ)]‐4,6‐iPr2‐C6H2) (2). UV/Vis and EPR spectroscopic studies showed that the latter reaction proceeds via initial SET, forming RIP [PTip3]⋅+[DDQ]⋅−, and subsequent homolytic C−H bond activation, which was supported by DFT calculations. The isolation of analogous products, Tip2P(H)(2‐[CMe2{TCQ−B(C6F5)3}]‐4,6‐iPr2‐C6H2) (4, TCQ=tetrachloro‐1,4‐benzoquinone) and Tip2P(H)(2‐[CMe2{oQtBu−B(C6F5)3}]‐4,6‐iPr2‐C6H2) (8, oQtBu=3,5‐di‐tert‐butyl‐1,2‐benzoquinone), from reactions of PTip3 with Lewis‐acid activated quinones, TCQ−B(C6F5)3 and oQtBu−B(C6F5)3, respectively, further supports the proposed radical mechanism. As such, this study presents key mechanistic insights into the homolytic C−H bond activation by the synergistic action of radical ion pairs.

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Complexation of B(C₆F₅)₃ and 9,10-Dicyanoanthracene: Dual Role of Borane as Spatial and Electronic Tuner

Cited by 7 publications

References 35 publications

Complexation‐Triggered Fluctuation of π‐Conjugation on an Antiaromatic Dicyanoanthracene Dianion

Complexation‐Triggered Fluctuation of π‐Conjugation on an Antiaromatic Dicyanoanthracene Dianion

B←N Coordination: From Chemistry to Organic Photovoltaic Materials

Homolytic C−H Bond Activation by Phosphine−Quinone‐Based Radical Ion Pairs

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