yrammuS 要概エチニルアクリジン修飾オルトカルボランより，固体状態で強いエキシマー発光が得られることを見出した．これまでに報告したエチニルピレン修飾オルトカルボランでは，77 Kという極低温化でしかエキシマー発光が見られなかったが，今回のアクリジン体では室温でも高い量子収率で発光が見られた．単結晶構造解析の結果，アクリジン部位の重なりが阻害されていることが明らかとなった．特に，アクリジン部位の窒素とオルトカルボランの水素との間で近接相互作用が見られたことから，ヘテロ環導入により分子運動が抑制され，室温でもエキシマー発光が得られたと考えられた．この結果は，エチニルオルトカルボラン部位が固体エキシマー発光団として働くことを示唆している．We report highly-efficient and solid-state excimer emission based on the acridine-o-carborane dyad possessing the ethynyl spacer. The previous pyrene-modified o-carborane showed excimer emission only at 77 K in the crystalline state, meanwhile the current acridine-modified molecule presented excimer emission with high efficiency (ΦPL = 0.23) in crystalline state at room temperature. From single crystal X-ray crystallography, it was indicated that two acridine moieties were stacked and the third acridine molecule was out of alignment. Such a packing mode could restrict exciton splitting over the columnar packing structure. Moreover, molecular interactions through the nitrogen atom in the acridine moiety and the hydrogen atom in the o-carborane unit contributes to suppression of molecular motions. As a consequence, improvement of emission efficiency was obtained.光散乱体深部において入射光を理想的な焦点として絞り込む補償光学の技術と，波長が長く，散乱されにくい超音波として分光学的信号を検出する光音響分光法とを組み合わせた新規分光装置を開発した．特に本装置では，波長が長く試料によって散乱されにくい近赤外光を光源として用い，対象の二光子励起によって生じる信号を計測することで，より到達深度の高い方法の実現を目指した．アガロースゲルで作製した試験試料へ応用した結果，光吸収体からの二光子励起光音響信号の検出と，補償光学的手法による信号強度の最適化に成功した．以上の結果から，さらなる深部顕微分光計測への途を拓いた．A micro-spectroscopic apparatus with high spatial resolution and molecular selectivity is developed. In the apparatus, a technique for adaptive optics, which enables the concentration of the incident light to the ideal focal spot in the deep part of the light-scattering sample, and photoacoustic spectroscopy, in which the spectroscopic signal from the sample is detected as the intensity of an acoustic wave deriving from the photoexcitation of the target molecule, are combined. In particular, in the developed apparatus, near-infrared light with long wavelength is utilized as the sample excitation, and the photoacoustic signal by the two-photon excitation of the sample is detectedfor application of measurement for more deeply buried samples. In the present study, the two-photon photoacousitic signal from a test sample is successfully detected, and the signal intensity is optimized with the method based on adaptive optics.田中 一生49Kazuo TANAKA伴野 元洋50Motohiro BANNO三次元共役ホウ素クラスター分子による機械的刺激応答性固体発光フィルムの開発 (2018年採択)Development of mechanochromic luminescent films based on steric conjugated boron cluster(Project 2018)補償光学二光子励起光音響分光装置の開発と光散乱体深部における分光計測 (2018年採択)Development of adaptive optic two-photon photoacoustic spectrometer and its application to samples deeply buried by scattering media(Project 2018)47Rep. Grant. Res., Asahi Glass Foundation (2019)
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