Triple Aza[6]helicenes with Circularly Polarized Luminescence: N-Alkylation as a Tool to Tune the Chiroptical Properties

doi:10.6023/cjoc202405006

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (9): 2841-2846.DOI: 10.6023/cjoc202405006 Previous Articles Next Articles

ARTICLES

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

夏羽菲, 江丽, 杨巧, 于琇, 陈丰坤^*()

东华大学材料科学与工程学院纤维材料改性国家重点实验室上海 201620

收稿日期:2024-05-07 修回日期:2024-05-17 发布日期:2024-05-23
通讯作者: 陈丰坤
基金资助:
国家自然科学基金(22171044)

Triple Aza[6]helicenes with Circularly Polarized Luminescence: N-Alkylation as a Tool to Tune the Chiroptical Properties

Yufei Xia, Li Jiang, Qiao Yang, Xiu Yu, Fengkun Chen()

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620

Received:2024-05-07 Revised:2024-05-17 Published:2024-05-23
Contact: Fengkun Chen
Supported by:
National Natural Science Foundation of China(22171044)

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Abstract

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

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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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Fig. & Tab. 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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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

Triple Aza[6]helicenes with Circularly Polarized Luminescence: N-Alkylation as a Tool to Tune the Chiroptical Properties

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Fig. & Tab. 7

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