圆偏振发光三重氮杂[6]螺烯: N-烷基化调控其手性光学性质

doi:10.6023/cjoc202405006

摘要/Abstract

近年来, 多重螺烯因其高度扭曲的共轭结构、有趣的光学性质以及特异的分子间相互作用等特性, 受到了广泛关注. 杂原子掺杂可进一步对多重螺烯分子的结构和光学性质进行有效调控. 通过分子内氧化反应构筑了第一例三重氮杂[6]螺烯分子. 单晶X射线衍射结果显示该分子具有高度扭曲的三维螺旋桨式结构. 与已报道的三重氧杂[6]螺烯相比, 三重氮杂[6]螺烯的荧光量子产率提高至5.5%, 而其吸收和发射不对称因子(|g_abs|和|g_lum|)也得以增强, 分别达1.2×10^－2和3.0×10^－3, 且通过N-烷基化进一步增强该三重氮杂[6]螺烯的稳定性和手性光学性质.

关键词: 螺烯, 掺杂多重螺烯, 手性拆分, 圆偏振发光, 烷基化

Recently, multiple helicenes have attracted enormous attention due to their exceptionally distorted conjugated architectures, appealing optical properties and unique spatial stacking patterns. The electronic and optical properties of multiple helicenes could be modulated by heteroatom doping. Herein, the first triple aza[6]helicene was reported by an intramolecular oxidation reaction, which exhibited highly distorted propeller-like geometry revealed by single crystal X-ray diffraction analysis. In comparison to the reported triple oxa[6]helicene, the triple aza[6]helicene demonstrated increased quantum yield (5.5%), and chiroptical properties with a |g_abs| value of 0.012 and a |g_lum| value of 3.0×10^－3. Furthermore, the stability and chiroptical properties of the triple aza[6]helicene could be enhanced by N-alkylation.

Key words: helicene, multiple heterohelicene, chiral resolution, circularly polarized luminescence, alkylation

引用此文

夏羽菲, 江丽, 杨巧, 于琇, 陈丰坤. 圆偏振发光三重氮杂[6]螺烯: N-烷基化调控其手性光学性质[J]. 有机化学, 2024, 44(9): 2841-2846.

Yufei Xia, Li Jiang, Qiao Yang, Xiu Yu, Fengkun Chen. Triple Aza[6]helicenes with Circularly Polarized Luminescence: N-Alkylation as a Tool to Tune the Chiroptical Properties[J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2841-2846.

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图/表 7

Figure 1. Chemical structures of triple oxa[6]helicene and triple aza[6]helicenes

Scheme 1. Synthetic route of triple aza[6]helicene 2

Figure 2. Single crystal structures of 2: (a) Top and side views of ORTEP drawing of (P,P,P)-2 with 50% probability thermal ellipsoids. (b) Packing structure of 2 Hydrogen atoms are omitted for clarity.

Scheme 2. Synthetic route of N-butylated triple aza[6]helicene 3

Compound	λ_abs^b/nm	λ_em^b/nm	^c/eV	Φ_PL^d/%	τ_s^e/ns	k_r^f/(10⁷ s^－1)	k_nr/(10⁸ s^－1)
TO6H^a	365	490/510	—	5.0	5.80	0.86	1.64
2	388	506/530	2.46	5.5	4.27	1.29	2.21
3	393	508/532	2.44	5.8	4.41	1.32	2.14

Table 1. Summary of the optical properties of 2 and 3

Figure 3. UV-vis absorption and fluoresence spectra of 2 and 3 in THF solution

Figure 4. CD and CPL spectra of the two enantiomers of (a) 2 and (b) 3 in THF solution

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