双（芳基硒基）BOPHYs的合成和三重态敏化；在三重态-三重态an灭上转换中的潜在应用,New Journal of Chemistry

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双（芳基硒基）BOPHYs的合成和三重态敏化；在三重态-三重态an灭上转换中的潜在应用
New Journal of Chemistry ( IF 2.7 ) Pub Date : 2021-3-12 , DOI: 10.1039/d1nj00721a
Ryohei Hasegawa _{1,

2,

3,

4,

5} , Shinji Iwakiri _{1,

2,

3,

4,

5} , Yuji Kubo _{1,

2,

3,

4,

5}

Affiliation

由于对开发新型三重态敏化剂的兴趣日益浓厚，在双（二氟硼）-1,2-双（（1 H-吡咯-2-基）亚甲基的2和7位上引入芳基硒基（ArSe）基团）研究了肼（BOPHY）支架用于生产染料1和2的过程。直接的Se–C键形成有效促进了系统间交叉（ISC）通道进入相应的三重态，并使它们具有三重态敏化作用。量子产率（Φ _Δ）单线态氧的（¹ Ò ₂使用diphenylisobenzofuran（DPBF）测定）的产生，导致优选的Φ _Δ的73％值和74％11和2分别显着高于卤化BOPHY。这归因于基于硒的重原子对BOPHY染料的光物理性质的影响，这是通过估算S ₁ →T _n跃迁的自旋-轨道耦合（SOC）值而合理化的。在光照射下产生¹ O ₂的良好能力促使我们将染料用作三重态-三重态an灭上转换（TTA-UC）的敏化剂。的甲苯溶液的光激发1（DPA）和9,10-二苯基蒽作为具有524纳米波长激光的三重态能量受体允许检测与上转换的发射λ _EM412 nm和430 nm的峰值，归因于DPA荧光。在UC工艺中观察到约94nm的显着的抗斯托克斯位移，其图片ID：d1nj00721a-t1.gif

为3.9％。这项研究表明，明智地将驴单位引入生色团为设计三重态敏化剂提供了一种简便而有效的策略。

"点击查看英文标题和摘要"

Synthesis and triplet sensitization of bis(arylselanyl)BOPHYs; potential application in triplet–triplet annihilation upconversion

Owing to the growing interest in the development of novel triplet sensitizers, the introduction of arylselanyl (ArSe) groups at the 2 and 7 positions of bis(difluoroboron)-1,2-bis((1H-pyrrol-2-yl)methylene) hydrazine (BOPHY) scaffold was investigated for producing dyes 1 and 2. Direct Se–C bond formation was effective in facilitating the intersystem crossing (ISC) channel to the corresponding triplet state, endowing them with triplet sensitization. The quantum yield (Φ_Δ) of the singlet oxygen (¹O₂) generation was determined using diphenylisobenzofuran (DPBF), resulting in preferable Φ_Δ values of 73% and 74% for 1 and 2, respectively, which were significantly higher than those of halogenated BOPHY. This was ascribed to the selenium-based heavy-atom effect on the photophysical properties of BOPHY dye, which was rationalized by estimating the spin–orbit coupling (SOC) values of the S₁ →T_n transitions. The favorable ability to generate ¹O₂ under photoirradiation motivated us to apply the dye as a sensitizer to triplet–triplet annihilation upconversion (TTA-UC). Photoexcitation of a toluene solution of 1 and 9,10-diphenylanthracene (DPA) as the triplet energy acceptor with a 524 nm-wavelength laser allowed to detect upconverted emission with λ_em values of 412 nm and 430 nm, which were attributed to the DPA fluorescence. A significant anti-Stokes shift of approximately 94 nm was observed in the UC process with a Image ID:d1nj00721a-t1.gif

of 3.9%. This study suggests that a judicious introduction of ArSe units into chromophores provides a facile but effective strategy for designing triplet sensitizers.

更新日期：2021-03-19

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